WO1992000588A1 - Optical disk - Google Patents

Optical disk Download PDF

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Publication number
WO1992000588A1
WO1992000588A1 PCT/JP1991/000886 JP9100886W WO9200588A1 WO 1992000588 A1 WO1992000588 A1 WO 1992000588A1 JP 9100886 W JP9100886 W JP 9100886W WO 9200588 A1 WO9200588 A1 WO 9200588A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
curable resin
resin composition
acrylate
optical disc
Prior art date
Application number
PCT/JP1991/000886
Other languages
French (fr)
Japanese (ja)
Inventor
Tsuneo Hagiwara
Utami Yonemura
Eiichi Hashimoto
Original Assignee
Teijin Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2172655A external-priority patent/JPH0467328A/en
Priority claimed from JP2172657A external-priority patent/JPH0467330A/en
Priority claimed from JP2172658A external-priority patent/JPH0467331A/en
Priority claimed from JP2172656A external-priority patent/JPH0467329A/en
Priority claimed from JP3033371A external-priority patent/JPH04247338A/en
Priority claimed from JP3033369A external-priority patent/JPH04247337A/en
Priority claimed from JP3033368A external-priority patent/JPH04247336A/en
Application filed by Teijin Limited filed Critical Teijin Limited
Publication of WO1992000588A1 publication Critical patent/WO1992000588A1/en

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Classifications

    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
    • G11B7/2542—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of organic resins

Definitions

  • the present invention relates to an optical disc that records and reproduces information using light such as a laser beam.
  • Optical discs are attracting attention as high-density, large-capacity information recording media, and various types of optical discs are being researched and developed. Among them, erasable and rewritable magneto-optical discs have a wide range of applications and great expectations for the future. Various materials and systems have already been announced and their practical use has begun.
  • optical discs need to be subjected to antistatic treatment to prevent dust and the like from adhering.
  • an antistatic agent is applied to the surface of the substrate, or the antistatic agent is kneaded into the substrate.
  • the former treatment has a problem in durability, and the latter treatment has problems in moldability and light transmittance.
  • the substrate of an optical disc is generally made of polycarbonate resin or the like, the surface hardness of the substrate is moderate. No. Therefore, it has been proposed to form a hard coat layer using a UV curable resin or the like as a surface hardening treatment to avoid surface damage.
  • a UV curable resin or the like as a surface hardening treatment to avoid surface damage.
  • the resin is charged due to friction with the air while the disk is rotating, and there are many dirt and dust on the read surface due to the adhesion of dust. There is a problem that reduces reliability.
  • the formation of the hard coat layer is performed in a clean room because the optical disc is extremely unlikely to adhere or mix foreign matter such as dust in terms of reliability. Under these constraints, the use of solvents and high temperatures is not preferred.
  • the present inventors have developed a low-viscosity curable resin composition which can be applied as a thin film even in a solvent-free manner from the above-mentioned objects, particularly from the viewpoint of coatability.
  • a curable composition containing a specific mono (meth) acrylate monomer has excellent surface hardness and low surface electric resistance, and has reached the present invention.
  • the present invention provides the following specific items of the first invention.
  • the present invention is based on a hard coat layer of an acrylic ester and comprises three inventions including two inventions of a hard coat layer of a composition derived therefrom.
  • the first invention provides an optical disc having a hard coat layer formed on at least a light irradiation surface (read surface), wherein the hard coat layer has the following formula (e):
  • R 1 and R 2 represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 23. ]
  • a second invention provides an optical disc having the same configuration as the first invention, wherein the hard coat layer has the following formula ( ⁇ ):
  • R 1 and R 2 represent a hydrogen atom or a methyl group
  • R 3 represents an alkyl group having 1 to 9 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 9 carbon atoms, A phenyl group substituted with an alkoxy group of
  • the third invention also provides an optical disc having the same configuration as the first invention, wherein the hard coat layer has the following formula ( ⁇ ) ft 1 R 2
  • R 1 and R 2 represent a hydrogen atom or a methyl group
  • n represents an integer of 1 to 23
  • m represents an integer of 1 or 2.
  • An antistatic composition obtained by curing a curable resin composition containing 0.1 to 60% by weight of a mono (meth) acrylate monodiphosphate compound of polyethylene glycol or polypropylene glycol represented by the following formula: Is a paint film An optical disc characterized by the above-mentioned.
  • the optical disc of the present invention includes a pit-type optical disc known as a compact disc ⁇ CD> composed of a recording medium having pits formed on a substrate made of glass, resin, or the like, and a thermal recording layer formed on the substrate. From a recording medium on which a bubble is formed by irradiating a laser beam, etc., and a bubble-tired optical disk that detects a level change based on a change in reflected light, or a recording medium on which a magneto-optical recording layer is formed on a substrate And other magneto-optical disks.
  • a pit-type optical disc known as a compact disc ⁇ CD> composed of a recording medium having pits formed on a substrate made of glass, resin, or the like, and a thermal recording layer formed on the substrate. From a recording medium on which a bubble is formed by irradiating a laser beam, etc., and a bubble-tired optical disk that detects a level change based on a change in reflected light, or
  • an organic resin substrate such as polycarbonate, polymethyl methacrylate, or amorphous polyolefin is used.
  • the recording surface of an optical disk is a surface on which a recording layer is formed on a substrate.
  • the surface opposite to the recording surface, that is, the light irradiation surface (read surface) is, for example, a flat surface without a groove formed on a magneto-optical disk.
  • a mono (meth) acrylic acid ester of polyethylene glycol or polypropylene dalicol of the formula (E) [In the present invention, the (meth) acrylic acid ester is an acrylic acid ester and Represents a methacrylic acid ester] as long as it has a necessary antistatic property.
  • the content when the antistatic property is imparted only with a mono (meth) acrylate of polyethylene glycol or polypropylene glycol of the formula (I) without containing an anionic surfactant or the like described below is 5 to 7 0% by weight is preferred, and more preferably 20 to 4% by weight, and if less than 5% by weight, the antistatic effect is insufficient, while if more than 70% by weight, the composition is coated and cured. The surface hardness of the resulting optical disc is insufficient, which is not preferable.
  • R 1 and R 2 in the formula (e) are a hydrogen atom or a methyl group, taking into account their UV curability, compatibility with the resin used in combination, and the surface electrical resistance and surface hardness of the cured product. Is chosen. n is an integer of 1 to 23, preferably 4 to 6. A (meth) acrylate in this range has the highest compatibility and gives a coating film having a low surface electric resistance.
  • the content of the ether derivative of the mono (meth) acrylate of polyethylene glycol or polypropylene glycol represented by the formula (H) in the curable resin composition is 5 to 70. % By weight, preferably from 10 to 60% by weight, particularly preferably from 15 to 50% by weight.
  • the compound is less than 5% by weight, the antistatic effect is insufficient, and on the other hand, it exceeds 70% by weight.
  • the surface hardness of the optical disk coated with the curable resin composition is insufficient, which is not preferable.
  • n is an integer of 5 to 23. Among them, n is preferably from 20 to 20. If n, which represents an alkylene glycol unit, is less than 5, the dalicol residue has low hydrophilicity and does not exhibit sufficient static elimination properties. On the other hand, if n exceeds 23, the solubility decreases, which is not preferable.
  • R 1 and R 2 represent a hydrogen atom or a methyl group
  • R 3 represents an alkyl group having 1 to 9 carbon atoms, a phenyl group, and a carbon number.
  • a phenyl group substituted with an alkyl group having 1 to 9 carbon atoms and a phenyl group substituted with an alkoxy group having 1 to 9 carbon atoms.
  • Examples of the alkyl group having 1 to 9 carbon atoms in R 3 include a methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl group and the like, which may be branched. Of these, a methyl, ethyl, propyl, or butyl group having 1 to 4 carbon atoms is preferred. Further, a phenyl group substituted with an alkyl group having 1 to 9 carbon atoms includes: Examples include diphenyl, butylphenyl, methylphenyl and the like.
  • Examples of the ether derivative of the mono (meth) acrylate ester of polyethylene daricol or polypropylene glycol represented by the formula (E) include:
  • CH 2 C-C0 (0CH 2 CH 2 ) a 0C 2 H 5
  • CH 2 CHC0 (0CH 2 CH 2 ) a 0C 2 H 5 CH 3
  • n 5 to 23
  • Pli represents a p-phenylene group.
  • CH 2 C-CO (OCH 2 CH 2 ) 8 OPI1C9 H19, but not limited thereto.
  • the content of the mono (meth) acrylate compound of the polyethylene (glycol) or polypropylene glycol represented by the formula (M) in the curable resin composition is 0.1 to 0.1%.
  • the amount is preferably 6% by weight, more preferably 0.2 to 50% by weight, and particularly preferably 0.5 to 50% by weight. ⁇ If the content exceeds 10% by weight, the surface hardness of the coated optical disk is insufficient, which is not preferable.
  • R 1, ⁇ . 2 is also hydrogen atom a methyl group
  • n represents an integer of 1 to 23
  • m is an integer of 1 or 2.
  • n is preferably 1 to 15 and particularly preferably 1 to 1.
  • a mono- or diphosphate compound of a ter compound for example,
  • CH 2 CH-C0 (0CH 2 CH) a 0P (0H) 2 CH 3
  • n represents an integer of from 0.1 to 23].
  • the phosphoric ester compound is an ethylene glycol mono (meth) acrylic acid ester phosphoric acid monoester compound of the formula ( ⁇ /), which is a 1: 1 adduct of an organic amine compound. Contained in curable resin composition By doing so, the antistatic performance and, consequently, the surface hardness can be improved.
  • the content of the adduct in the curable resin composition is from 0.1 to '20% by weight, preferably from 0.2 to 15% by weight, particularly preferably from 0.5 to 10% by weight. If the amount of the adduct is less than 0.1% by weight, the antistatic effect is insufficient, while if it exceeds 20% by weight, it becomes difficult to be compatible with the curable resin, which is not preferable from the viewpoint of coatability.
  • CH 2 C- C00CH 2 CH 2 OP (OH) 2 /
  • CH 2 C- COOCH2 CH 2 OP (OH) 2 /
  • CH 2 C- C00CH 2 CH 2 N (C 2 H 5 ) 2
  • CH 2 C- COOCH2 CH 2 0P (0H) 2 / H 2 N CH 2 CH 2 OH CH 3
  • CH 2 C- COOCH2 CH 2 0P ⁇ 0H ⁇ 2 Z (C 2 H 5 ) 3 N And the like.
  • polymerizable monomers polymerizable oligomers
  • polymerizable copolymers are used.
  • Multifunctional oligoester acrylate polyfunctional polyacrylate, acrylate modified phosphazene compound, polyfunctional acrylate of isocyanuric acid, etc.
  • Use may be made of vinyl polymerizable compounds, acrylic polymerizable compounds, etc. These polymerizable compounds may be used alone or as a mixture.
  • the curable resin composition of the present invention is used by adding a radical polymerization initiator such as a photopolymerization initiator and a thermal polymerization initiator, if necessary.
  • a radical polymerization initiator such as a photopolymerization initiator and a thermal polymerization initiator
  • the antistatic performance and A curable resin composition having the following composition is preferred from the viewpoint of both surface hardness and surface hardness, and further from the viewpoint of film forming properties.
  • the (meth) acrylic acid ester of the formula (I) has n of 4 to 6, and the other components of the curable resin composition include dipentaerythritol hexaacrylate or its allolactone. It is a curable resin composition comprising a modified product, if necessary, a polymerizable diluent other than these, and a polymerization initiator.
  • Dipentaerythritol hexacrylate or its modified allolactone is suitable in that it has relatively low clay and high curability, and among these, the modified allolactone is more preferable.
  • the modified force allolactone is represented by the following formula.
  • CA30, DPCA60, and DPCA120 are dipentaerythritols modified with 2, 3, 6, and 12 molecules of force prolactone, respectively, on average, and have low skin irritation and low odor.
  • the curing speed is extremely fast, and the cured product is Since it shows flexibility despite its high hardness, it gives cured products with excellent weather resistance. Furthermore, since the viscosity is low, the coatability is good when the composition is formed.
  • the content of this component in the curable resin composition is 40 to 80% by weight, preferably 50 to 80% by weight. Above this, the surface electric resistance of the coating film is undesirably high. In addition, if it is lower than that, it is not preferable because the surface hardness of the coating film cannot be increased.
  • the polymerizable diluent is used as needed for the purpose of lowering the viscosity at the time of applying the curable resin composition. Therefore, low-viscosity (meth) acrylates having 1 to 3 functionality are used.
  • Component (a) the (meth) acrylate and component (b) the dipentaerythr Retile (meta) Depends on the type and composition of acrylate
  • a (meth) acrylate having a viscosity of 10 vise or less, preferably 5 poise or less, at 25 C measured by a 13-type viscometer is used.
  • hexamethylene glycol diacrylate, tetrahydrofurfuryl acrylate, hexamethylene glycol dimethacrylate, tetrahydrofurfuryl methacrylate, and trimethylethyl-1-fluoropropria Preferably used are acrylate, neopentyl glycol hydroxypivalate, glyceryl dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, and pentaerythritol tetraacrylate.
  • hexamethylene glycol diacrylate and tetrahydrofuryl acrylate are particularly suitably used for improving the adhesion of the cured product to the polycarbonate substrate and adjusting the viscosity of the composition.
  • the amount of the polymerizable diluent used as the component (c) is 0 to 40% by weight, preferably 0 to 30% by weight of the curable resin composition including the case where it is not used. Above that, the surface hardness increases depending on the type, but the surface electric resistance does not decrease and the adhesion to the substrate is deteriorated. Thus, the polymerization initiator is not preferable.
  • Acrylic The acid ester, the dipentaerythritol (meta) acrylate of the component (b), and the polymerizable diluent of the component (C) are preferably 0.1 to 10 phr (weight.part per hundred resin) based on the total weight. Is 0.5 to 7 phr, more preferably 2 to 5 phr.
  • photopolymerization initiator examples include benzophenone-based initiators such as benzophenone and Michler's ketone; diketone-based initiators such as benzyl and phenylmethoxydiketone; acetphenone-based initiators such as acetophenone; benzoinethyl ether and benzyldimethine.
  • Benzoin-based initiators such as / reketane / re, thioxanthone-based initiators such as 2,4-getylthioxanthone, and quinone-based initiators such as 2-methylanthraquinone and camphorquinone are preferably used.
  • an accelerator such as an amine accelerator can be used in combination.
  • azobisdisbutyronitrile ⁇ AIBN> benzoylperoxide (BPO), cumene hydroperoxide, dicumyl peroxyloxide, dibutyl butylperoxide Oxide, peryl yl beloxide and the like.
  • anionic surfactant saturated and non-saturated Saturated fatty acid metal salts, saturated or unsaturated aliphatic sulfonates, aromatic sulfonates that may have substituents, sulfonates containing ethylene glycol units, and sulfur containing various substituents —Salt sodium salt.
  • anionic surfactants saturated and non-saturated Saturated fatty acid metal salts, saturated or unsaturated aliphatic sulfonates, aromatic sulfonates that may have substituents, sulfonates containing ethylene glycol units, and sulfur containing various substituents —Salt sodium salt.
  • fatty acid tests such as sodium alkyl ether sulfonate, alkyl sulfate sodium salt, sodium alkyl ether sulfate, potassium oleate and potassium coconut fatty acid, among which sulfonic acid salt compounds and sulfate ester salt compounds are preferred. Good.
  • the content of the anionic surfactant is determined by the formula of the component (a).
  • (I) 0.01 to 200% by weight, more preferably 0.1 to 200% by weight, based on the amount of the (meth) acrylic acid ester in (I).
  • (meth) acrylate of the component (a), dipentaerythritol of the component (b) and the component (c) )) Is 0.0 ° to 1 to 10% by weight based on the total weight of the polymerizable diluent.
  • the content of the component (a) in the curable resin composition is determined when the component (e) is not used.
  • the preferred range is from 3 to 40% by weight, and the component (a) is less than 3% by weight.
  • the curable resin composition of the present invention described above can coat the surface of the optical disc by a known spin coating method, dip coating method, coating with a doctor knife, or a method with a bar coater.
  • the spin coating method is practically most preferable because the film thickness is easily controlled.
  • covering the side surface of the optical disk also improves the antistatic effect.
  • the viscosity of the curable resin composition is measured at 25 C using a B-type viscometer. Is less than 20 boys, preferably less than 10 boys, more preferably less than 5 boys. Above that, it is not preferable because the coating film cannot be controlled smoothly.
  • the thickness of the cured coating film of the present invention is 1 to 30 m, preferably 5 to 25 m. If it is lower than this, sufficient performance is not exhibited in terms of hardness, and if it is higher than this, not only is it difficult to control the film thickness, but also the internal curability decreases, which is not preferable.
  • the optical disk coated with the composition is cured by known methods and conditions using an active lamp such as an ultraviolet lamp such as a low-pressure mercury lamp, a medium-pressure mercury lamp, and a high-pressure mercury lamp, a halogen lamp, an electron beam, or a heat treatment. .
  • an active lamp such as an ultraviolet lamp such as a low-pressure mercury lamp, a medium-pressure mercury lamp, and a high-pressure mercury lamp, a halogen lamp, an electron beam, or a heat treatment.
  • actinic rays such as an ultraviolet lamp, a halogen lamp, and an electron beam from the viewpoint of operability and productivity.
  • the antistatic property in the present invention may be any as long as foreign substances such as dust and dust do not adhere to the surface. This is displayed in detail on the surface resistivity, 1 0 1 5 ⁇ ⁇ ⁇ less than the optical disc, preferably it is said that less than 1 0 1 4 ⁇ ⁇ ]. It is said that the surface hardness must be small enough not to cause scratches due to normal handling, specifically cleaning the surface with a cloth, or catching with a nail. 'Specifically, this can be represented by the pencil hardness specified in JIS standard, and is generally HB or more, preferably F or more. In the present invention, these are used as criteria. As described above, the present invention can provide an optical disc having an antistatic ability with a high degree of durability and a sufficient surface hardness. BEST MODE FOR CARRYING OUT THE INVENTION
  • the surface resistance () is J I S K
  • the pencil hardness was measured using a Mitsubishi Pencil-made unit. Parentheses after the compound indicate the names of commercial products actually used and the manufacturer's name.
  • a curable resin composition (NSC-710, manufactured by Nippon Seika Co., Ltd.) and the following various objects (meta) are placed on the flat surface of a polycarbonate substrate with a thickness of 1.2 mm and a diameter of 13 OM.
  • Acrylic ester, its phosphoric ester, or a mixture of a 1: 1 adduct of it and an organic amine compound with each of the copolymerized monomers is applied by spin coating to a thickness of about 1 O ⁇ tm.
  • ultraviolet rays were irradiated from a height of 20 cm for 1 minute using a high-pressure mercury lamp of about 27 cm in length and 2 Kw to cure the coating film.
  • CH 2 C- C00CH 2 CH 2 0P (0H) 2 /
  • CH 2 C- C00CH 2 CH 2 N (CH 3) 2
  • CH 2 C- C00CH 2 CH 2 0P (0H) 2 /
  • CH 2 C- COOCH2 CH 2 0P (0H) 2 / H 2 NCH 2 CH 2 OH
  • Comparative Example 1 was a case where the copolymerized monomer was not added, and Comparative Example 2 was a solution in which a kneading-type antistatic agent sorbitan laurate (Newcol 20, manufactured by Nippon Emulsion Co., Ltd.) was dissolved in alcohol on a polycarbonate substrate. And apply, dry It is a thing.
  • a kneading-type antistatic agent sorbitan laurate Newcol 20, manufactured by Nippon Emulsion Co., Ltd.
  • the surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • Hexafunctional urethane acrylate oligomer (U1226, manufactured by Shin-Nakamura Chemical Co., Ltd.) 40% by weight, Hexafunctional acrylate oligomer (KAY AR AD DPCA60, manufactured by Nippon Kayaku Co., Ltd.) 20% by weight, and tetraethylene glycol mono Methacrylate (Blemmer PE 200, manufactured by Nippon Oil & Fats Co., Ltd.) 40% by weight, photoinitiator ⁇ -hydroxyisobutylphenone (Darocur 1 173, manufactured by Merck) 3 Phr of curable resin composition of thickness 1
  • a flat surface of a polycarbonate substrate having a diameter of 2 mm and a diameter of 13 ⁇ M was applied to a thickness of about 1 ⁇ m by a spin coating method, and was photocured in the same manner as in Examples 1-21.
  • the surface hardness of the cured surface of the substrate was HB, and the surface resistance was 2.1 ⁇ 10 13 ⁇ . ⁇ .
  • Hexaacrylate of phosphazene (U-1000, Made by Idemitsu Petrochemical Co., Ltd.> 40% by weight, tetraaropyrene glycol monomethacrylate ⁇ Blemmer PP—
  • a curable resin composition consisting of 330%, manufactured by Nippon Oil & Fat Co., Ltd., 60% by weight, and a photoinitiator, Irgaki Yua 907 (manufactured by Ciba Geigy Co., Ltd.), 5 phr, was applied to a polycarbonate substrate in the same manner as in Example 22,
  • the cured coating film had a surface hardness of HB and a surface resistance of 3.6 X 10 ⁇ / ⁇ .
  • Hexaacrylate of phosphazene (U-100, manufactured by Idemitsu Petrochemical Co., Ltd.) 30% by weight, tetraethylene glycol monomethacrylate (Blemma 1-200, manufactured by NOF Corporation) 70% by weight, Photoinitiator Irgacure
  • a curable resin composition consisting of 5 phr was applied to a polycarbonate substrate in the same manner as in Example 22 and light-cured.
  • the surface hardness of the cured coating film was HB and the surface resistance was 5.3 X 10 ⁇ ⁇ .
  • Hexaacrylate of phosphazene (U-100, manufactured by Idemitsu Petrochemical Co., Ltd.) 80% by weight, tetraethylene glycol monometaacrylate (Blenmer 200, manufactured by NOF Corporation) 2% by weight, AIBN A curable resin composition of 5 phr was coated on a polycarbonate substrate according to Example 22. And heat cured at 80. The surface hardness of the cured coating film was F and the surface resistance was 6.3 X 10 14 ⁇ ,
  • Phosphazene to the Kisaakurireto (U- 1 000, manufactured by Idemitsu Petrochemical Co., Ltd.> 80 wt%, main butoxy tetraethylate les glycol monomethacrylate ⁇ methacrylonitrile rate 20 wt%, implementing a curable resin composition comprising AIBN 5 P hr Example 2
  • the composition was applied on a polycarbonate substrate and thermally cured in the same manner as in 5.
  • the cured film had a surface hardness of F and a surface resistance of 7.3 ⁇ 10 14 ⁇ / ⁇ .
  • Hexafunctional urethane acrylate oligomer (U1226A manufactured by Shin-Nakamura Chemical Co., Ltd.) 4% by weight, hexafunctional acrylate oligomer (KAY ARAD DPCA 60, manufactured by Nippon Kayaku Co., Ltd.) 20% by weight, and tetraethyleneglycol A curable resin composition consisting of 40% by weight of luminomethacrylate (Light Ester DM, manufactured by Kyoeisha Oil & Fats Co., Ltd.) and 3 phr of photoinitiator Darocure 1173 (manufactured by Merck) was applied to a polycarbonate substrate in the same manner as in Example 22.
  • the coated and photocured disk had a surface hardness of F and a surface resistance of 11 ⁇ 10 12 ⁇ 1.
  • Hexaacrylate of phosphazene (U-1 000, manufactured by Idemitsu Petrochemical Co., Ltd.) 55% by weight of monoethylene glycol phosphate methacrylate (light ester DM, manufactured by Kyoeisha Oil Co., Ltd.) 45% by weight, photoinitiator Irgacure 9 ⁇ 7 (manufactured by Ciba-Geigy Corporation)
  • a curable resin composition consisting of 5 plir was applied to a polycarbonate substrate and light-cured in the same manner as in Example 22.
  • the surface hardness of the cured coating was HB and the surface resistance was 3 8X 10 10 ⁇ .
  • Hexaacrylate of phosphazene (U-1000, manufactured by Idemitsu Petrochemical Co., Ltd.) 95% by weight of monoethylene glycol methacrylate phosphate (light ester DM, manufactured by Kyoeisha Oil & Fat Co., Ltd.) 5% by weight, radical initiator AI BN
  • a curable resin composition consisting of 5 phr was applied to a polycarbonate substrate and thermally cured in the same manner as in Example 25.
  • the surface hardness of the cured coating film was HB and the surface resistance was 5.2 ⁇ 10 14. ⁇ ].
  • Hexafunctional urethane acrylate oligomer (U1226, manufactured by Shin-Nakamura Chemical Co., Ltd.) 40% by weight, hexafunctional acrylate oligomer (KAYARAD DPCA 60, manufactured by Nippon Kayaku Co., Ltd.) 40% by weight, and tetraethylene glycol Lumonomethacrylate (Phosmer M, manufactured by Kyoeisha Yushi Co., Ltd.) 20% by weight, photoinitiator Darocure 1 173 (manufactured by Merck)
  • a curable resin composition consisting of 3 phr was applied to a polycarbonate substrate in the same manner as in Example 22.
  • the surface hardness of the obtained disk was HB, and the surface resistance was 1.1 ⁇ 10 ⁇ , / ⁇ .
  • Hexaacrylate of phosphazene (U-1000, manufactured by Idemitsu Petrochemical Co., Ltd.) 99% by weight of monoester of ethylene glycol monomethacrylate and triethylamine 1: 1 adduct 1% by weight, photoinitiator Irgacure
  • a curable resin composition consisting of 5 phr was applied to a polycarbonate substrate in the same manner as in Example 22 and light-cured.
  • the surface hardness of the cured coating film was 3H, and the surface resistance was 8.5 ⁇ 10 14 ⁇ square.
  • Hexaacrylate of phosphazene (U-1000, manufactured by Idemitsu Petrochemical Co., Ltd.) 99.5% by weight of phosphoric acid monoester of ethylene glycol monomethacrylate and triethylamine 1: 1 adduct 0.5% by weight and AIBN 5
  • a curable resin composition composed of Phr was applied on a polycarbonate substrate in the same manner as in Example 25, and was thermally cured. Hardening The surface hardness of the coating film was 3H, and the surface resistance was 9.5 ⁇ 10 14 ⁇ ⁇ .
  • tetraethylene diol monoacrylate represented by the formula: 20% by weight of DPCA 60 and 20% by weight of DPCA 30 as dihexaerythritol hexyl acrylate.
  • the viscosity of this composition was 25 using a B-type viscometer.
  • the value of C was 1.3 voise.
  • This composition was applied to a flat surface of a polycarbonate substrate having a thickness of 1.2 mm and a diameter of 130 mm by a spin coating method so as to have a thickness of 8 m. Subsequently, using a high-pressure mercury lamp of about 27 cm in length and 2 KW, ultraviolet light was irradiated for 1 minute from a height of 20 cm to cure the coating film.
  • the surface resistance and pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface pencil hardness is H
  • the surface resistivity was 1.
  • the substrate with the cured coating film was subjected to a weather resistance test in a humidifier at 80 or 85% humidity. After 2000 hours, no change was observed in the cured coating before and after the test.
  • hexaethylene dalicol monoacrylate represented by the following formula: 30% by weight of DPCA 120 and 20% by weight of DPCA 20 as dialloerythone-modified dipentaerythritol hexaacrylate, and 20% by weight of dipentaerythritol hexaacrylate.
  • a curable resin composition containing 10% by weight of xamethylene glycol diacrylate and a photoinitiator Irgacure 907 (manufactured by Ciba Geigy Co., Ltd.) for 5i> hr was prepared, and the viscosity of the composition was B-type. As measured at 25 C with a viscometer, the result was' 1.1 vois.
  • This composition was applied to a polycarbonate substrate in the same manner as in Example 33 so as to have a thickness of 1 Om, and was light-cured.
  • Example 33 so as to have a thickness of 1 Om, and was light-cured.
  • the surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface hardness of the hardened surface is H and the surface resistance is 6.5 X
  • a curable resin composition containing 3 p r of a photopolymerization initiator Irgacure 907 (manufactured by Ciba-Geigy Co., Ltd.) in a composition consisting of 10% by weight of lugia acrylate was prepared, and the viscosity of the composition was measured at 25 ° C using a B-type viscometer. This composition was applied to a polycarbonate substrate in the same manner as in Example 34, and was cured by light.
  • the surface resistance and pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface hardness of the cured surface was F, and the surface resistance was 1. IX 10 13 ⁇ 1.
  • a photopolymerization initiator was added to a composition comprising 30% by weight of tetraethylene dalicol monoacrylate represented by the following formula, 35% by weight of DPCA 60 and 35% by weight of DPCA 30 as a hexaolactone-modified dipentaerythritol hexaacrylate.
  • a curable resin composition containing 3g of Irgacure 907 (manufactured by Ciba Geigy) was prepared. Of this composition The viscosity was measured at 25 using a B-type viscometer and found to be 2.1 vois. This composition was applied to a polycarbonate substrate in the same manner as in Example 34, and photocured.
  • the surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface hardness of the obtained cured surface was F, and the surface resistance was 4.3 ⁇ 10 13 ⁇ 1.
  • the surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface hardness of the hardened surface is F and the surface resistance is 5.8 X
  • a curable resin composition containing 3 Phr of a photopolymerization initiator Darocure 1 173 (manufactured by Merck) in a composition consisting of 10% by weight of mono-diacrylate was prepared. It was 0.98 boise at a measurement of 5 ° C. This composition was applied to a polycarbonate substrate in the same manner as in Example 34 and photocured.
  • the surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface hardness of the cured surface was F, and the surface resistance was 4. IX 10 13 ⁇ 1.
  • hexene ethylene diol monoacrylate represented by the following formula: 30% by weight of DPCA 60 and 2% by weight of DPCA 30 as a hexaolacrylate modified dipentaerythritol hexaacrylate; 20% per liter pantoliac acrylate, tetrahydrofurfurfuryl
  • a curable resin composition containing 3 phr of a photopolymerization initiator Irgacure 907 manufactured by Ciba-Geigy Corporation
  • the viscosity of this composition was 1.1 Boys as measured at 25 C by a B-type viscometer. This composition was applied to a polycarbonate substrate in the same manner as in Example 34, and photocured.
  • the surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface hardness of the cured surface was H, and the surface resistance was 6.5 ⁇ 10 ′′ b.
  • hexaethylene glycol monoacrylate represented by the following formula: 30% by weight of DPCA 60 and 35% by weight of DPCA 20 as a dialloerythone-modified dipentaerythritol hexaacrylate, neopentylglycol-l-diacrylate 1 ⁇ % by weight
  • a curable resin composition containing 4 Phr of a photopolymerization initiator Irgacure 907 manufactured by Ciba-Geigy Co., Ltd.
  • the viscosity of this composition was measured at 25 ° C using a B-type viscometer.
  • the composition was 2.3 poises ..
  • the composition was applied to a polycarbonate substrate and light-cured in the same manner as in Example 34.
  • the surface hardness of the cured surface was F, and the surface resistance was 6.9 ⁇ 10 13 ⁇ .
  • tetraethylene dimethyl monomethacrylate represented by the following formula: 50% by weight of DPCA120 as a dialloerythone-modified dipentaerythritol-hexahexyl acrylate, and 10% by weight of neopentyldaricol diacrylate hydroxypivalate
  • a curable resin composition containing 5 phr of a photopolymerization initiator Irgacure 907 (manufactured by Ciba-Geigy Corporation) in a composition consisting of 10% by weight of glycerol and 10% by weight of glycerol / dimethacrylate was prepared. The viscosity was measured by a B-type viscometer at 25. The measured viscosity at C was 2.6 V. This composition was applied to a polycarbonate substrate in the same manner as in Example 34, and photocured.
  • the surface resistance and pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface hardness of the hardened surface is F and the surface resistance is 9.8 X
  • a composition comprising 30% by weight, 60% by weight of DPCA 60 as a dialloerythrone-modified dipentaerythryl hexacrylate, and 10% by weight of pentaerythritol tetraacrylate is added to a photopolymerization initiator Irgacure 907 (manufactured by Ciba Geigy Corporation)
  • Irgacure 907 manufactured by Ciba Geigy Corporation
  • a curable resin composition containing 3 pl of was prepared. The viscosity of this composition was 3.3 Boyes as measured by a B-type viscometer in 2 steps. This composition was applied to a polycarbonate substrate in the same manner as in Example 34 and photocured.
  • the surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface hardness of the cured surface was H, and the surface resistance was 2.8 ⁇ 10 13 ⁇ 1.
  • tetrapropylene glycol monoacrylate represented by the following formula: 60% by weight of DPCA 60 as a hexaacrylate of dipentaerythritol modified with force allolactone
  • the surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface hardness of the hardened surface is F and the surface resistance is 5.8 X
  • a curable resin composition containing 3 phr of a photopolymerization initiator il Gacure 9 ⁇ 7 (manufactured by Ciba Geigy Co., Ltd.) in a composition consisting of 20% by weight was prepared using a B-type viscometer. 25. The measured value of C was 3.3 V.
  • This composition was placed on the flat surface of a polycarbonate substrate having a thickness of 1.2 mm and a diameter of 130 mm in the same manner as in Example 33. m to a thickness of 20 m, and then apply UV light from a height of 20 cm for 1 minute using a high-pressure mercury lamp of about 27 cm in length and 2 KW to illuminate the coating film. Cured.
  • the surface resistance and pencil hardness of the cured surface of the cured polycarbonate disk were measured. As a result, the surface pencil hardness was H, and the surface resistance was 6.5 ⁇ 10 15 ⁇ 3.
  • Curing resin composition (NSC-7106, manufactured by Nippon Seika) 96% by weight on the flat surface of a polycarbonate substrate with a diameter of 130mm and a diameter of 130mm, the following compound (MA150, Nippon Emulsifier)
  • MA150 Nippon Emulsifier
  • a mixture of 4% by weight of a composition containing 0.1 phr of sodium dodecyl benzene sulfonate was applied by spin coating to a thickness of 10 m in the same manner as in Example 34.
  • Ultraviolet rays were irradiated for 1 minute from a height of 20 cm using a high-pressure mercury lamp of about 27 cm and 2 Kw, and the coating was photocured.
  • a curable resin composition (NSC-7106, manufactured by Nippon Seika) was 96% by weight, and the compound described in Example 44 (MA 1 50, 4% by weight of Japan Emulsifier Co., Ltd.
  • the product was applied by spin coating to a thickness of 10 m in the same manner as in Example 44, and then UV rays were applied from a height of 20 cm using a high-pressure mercury lamp of about 27 cm in length and 2 Kw.
  • the coating was light cured for 1 minute.
  • the surface resistance and pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the pencil hardness was H, but the surface resistance was 1.2 ⁇ 10 15 ⁇ ⁇ 1.
  • Hexafunctional urethane acrylate oligomer (U1226 ⁇ , manufactured by Shin-Nakamura Chemical Co., Ltd.) 50% by weight, trimethylol aropan triacrylate 40% by weight, and tetraethylene glycol monomethacrylate 10% by weight
  • a curable resin composition containing 1 phr of sodium todecylbenzenesulfonate and 3 phr of a photoinitiator Darocure 1173 (manufactured by Merck) was applied to the polycarbonate substrate in the same manner as in Example 34.
  • the cured surface of the substrate had a surface hardness of F and a surface resistance of 3.6 ⁇ 10 13 ⁇ .
  • Hexafunctional urethane acrylate oligomer (U1226 ⁇ , manufactured by Shin-Nakamura Chemical Co., Ltd.) 50% by weight, trimethylol aropantriacrylate 40% by weight, and tetrae 1 phr weight of Tylendalcol monomethacrylate, 3 phr of Darocur 1 173 (manufactured by Merck) photoinitiator
  • the curable resin composition was applied to a polycarbonate substrate in the same manner as in Example 45. Coated and light cured. Surface hardness of the cured surface of the substrate is F, surface resistance 1. 0 5 ⁇ 1 0 15 ⁇ 1 der ivy.
  • Hexaacrylate of phosphazene (U-1 000, manufactured by Idemitsu Petrochemical Co., Ltd.) 70% by weight, tetrapropylene d'alicole monomethacrylate 30% by weight, Avanel
  • the curable resin composition comprising PhK and 3 phr of photoinitiator Irgacure 907 (manufactured by Ciba-Geigy Co., Ltd.) was prepared in the same manner as in Example 34. It was applied to a bottle substrate and light cured. The surface hardness of the cured coating film was H and the surface resistance was 3.5 ⁇ 10 12 ⁇ .
  • Tetraethylene dalicol monoacrylate represented by
  • a curable resin composition containing 0.5% by weight of sodium dodecylbenzenesulfonate and 3pr of a photopolymerization initiator Irgacure 907 (manufactured by Ciba-Geigy Corporation) was prepared in a composition consisting of 10% by weight.
  • the B-type viscosity was measured to be 1.9 vois by measurement at 25.
  • the composition was spin-coated to a thickness of 10 mm, as in Example 34, to a thickness of 10 jum. Apply it to the flat surface of a polycarbonate substrate with a diameter of 13 OM, and then irradiate ultraviolet rays for 1 minute from a height of 2 Ocm using a high-pressure mercury lamp of about 27 cm in length and 2 KW to harden the coating. It was. The surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface pencil hardness at H, the surface resistance 2. were 6 X 1 ⁇ 13 ⁇ 1.
  • the substrate having the cured product coating film was subjected to a weather resistance test for 2000 hours in a wet heat tester at 8 CTC and 85% humidity, but no change was observed in the cured coating film before and after the test.
  • tetraethylene dalicol monoacrylate represented by the following formula: 30% by weight of DPCA60 and 30% by weight of DPCA30 as a dialloerythone-modified dipentaerythrylhexaacrylate, 20% by weight of dipentaerythryl-hexaacrylate, 20% by weight of hexamethylene glycol recall di ⁇ chestnut rate 1 0 wt% composition comprising and a photopolymerization initiator Irugakyua 907 (Ciba-Geigy Ltd. one company) and 3-curable resin composition comprising P r was prepared.
  • This composition was applied to a polycarbonate substrate as in Example 48 and photocured.
  • the surface resistance and pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • a curable resin composition was prepared which contained 10% by weight of xamethylene dimethyl alcohol, 1 phr of sodium dodecylbenzenesulfonate and 5 Phr of a photopolymerization initiator irgacure 907 (manufactured by Ciba-Geigy Corporation). The viscosity of this composition was 1.7 voise as measured by a B-type viscometer at 25.
  • This composition was applied to the flat surface of a polycarbonate substrate by spin coating so as to have a thickness of 10> am in the same manner as in Example 34, and then a high-pressure mercury lamp of about 27 cm in length and 2 KW was used. Ultraviolet rays were irradiated from a height of 20 cm for 1 minute to photo-cur the coating film. The surface resistance and pencil hardness of the cured surface of the polycarbonate substrate after curing were measured.
  • the surface hardness of the cured surface was H, and the surface resistance was 1.5 ⁇ 10 13 ⁇ / 0.
  • a curable resin composition containing 5 phr of a photopolymerization initiator Irgacure 907 (manufactured by Ciba Geigy Corporation) in a composition comprising 10% by weight of acrylate was prepared.
  • the composition was 1.7 voices as measured at 25 ° C. This composition was applied to a polycarbonate substrate in the same manner as in Example 49 and photocured.
  • the surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface hardness of the cured surface was H, and the surface resistance was 1.5 ⁇ 10 15 ⁇ 3.
  • pentaethyleneglycol monoacrylate represented by the following formula: 45% by weight of DPCA 60 as a di-proerythritol-modified hexacrylate, and 20% by weight of DPCA 30 as trihexyrolitol triacrylate
  • DPCA 60 a di-proerythritol-modified hexacrylate
  • DPCA 30 a trihexyrolitol triacrylate
  • a composition comprising 20% by weight of hexamethylene darico-diacrylate and 10% by weight of Sodium kill ether sulfonate (Avanel S70; manufactured by NOF Corporation) l phr, photopolymerization initiator irgacure
  • a curable resin composition containing 3 piir of 907 (manufactured by Ciba-Geigy Co., Ltd.) was prepared, and the viscosity of the composition was 2.1 Boys as measured at 25 C using a B-type viscometer.
  • the surface resistance and pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the surface hardness of the cured surface was H, and the surface resistance was 3. IX 10 13 ⁇ ].
  • the surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
  • the present invention provides a hard coat layer for an optical disk such as a well-known compact disk (CD) and a magneto-optical disk that has been put into practical use, and has an antistatic performance with excellent durability and a required surface hardness. It has a hard coat layer that can be formed even without solvent. It is required to have a high degree of reliability, especially for the auxiliary storage device of computers where it is essential to prevent the adhesion of foreign substances such as dust and dust. It is suitable for an optical disk such as a magneto-optical disk.

Abstract

An optical disk with a low surface resistance and an excellent scuff resistance, wherein at least the surface to be irradiated with light is covered with a hard coating layer comprising an antistatic coating formed by curing a curable resin composition comprising at least one of mono(meth)acrylates of polyethylene glycol and polypropylene glycol represented by formula (I) wherein R?1 and R2¿ represent each hydrogen or methyl and n represents an integer of 1 to 23.

Description

明 細 書 発明の名称  Description Name of Invention
光ディスク 技術分野  Optical disc technical field
木発明は、 レーザ一などの光により、 情報の記録、 再 生を行う光ディスクに閬する。 背景技術  The present invention relates to an optical disc that records and reproduces information using light such as a laser beam. Background art
光ディスクは、 高密度 · 大容量の情報記録媒体と して 注目され、 種々のタイアの光ディスクの研究開発が行わ れている。 これらの中で、 消去可能で書換え可能な光磁 気ディスクは利用分野が広く、 将来への期待も大きく、 既に、 種々の材料 · システムが発表されており、 その実 用化も始まっている。  Optical discs are attracting attention as high-density, large-capacity information recording media, and various types of optical discs are being researched and developed. Among them, erasable and rewritable magneto-optical discs have a wide range of applications and great expectations for the future. Various materials and systems have already been announced and their practical use has begun.
これらの光ディスクには、 ホコリなどの付着を防止す るために帯電防止処理を行う必要があり、 通常は基板の 表面に帯電防止剤を塗工したり、 帯電防止剤の基板への 練り込みによる方法などがとられている， しかし、 前者 の処理では耐久性に問題があり、 後者では成型牲、 光透 過性の点で問題がある。  These optical discs need to be subjected to antistatic treatment to prevent dust and the like from adhering. Usually, an antistatic agent is applied to the surface of the substrate, or the antistatic agent is kneaded into the substrate. However, the former treatment has a problem in durability, and the latter treatment has problems in moldability and light transmittance.
一方、 光ディスクの基板は一般的にはポリカーボネー ト樹脂などが闬いられるために、 基板の表面硬度がノ j、さ い。 そこで、 表面の損傷を避けるために表面硬化処理と して U V硬化樹脂などによりハードコ一ト層を形成する ことが提案されている。 しかし、 これらの U V硬化樹脂 の塗工による被覆では、 ディスクの回転中の空気との摩 擦による樹脂の帯電があり、 ゴミ、 ホコリの付着による 読み出し面の汚れなどが多く、 記録、 読み出し信号の信 頼性を低下させる問題がある。 On the other hand, since the substrate of an optical disc is generally made of polycarbonate resin or the like, the surface hardness of the substrate is moderate. No. Therefore, it has been proposed to form a hard coat layer using a UV curable resin or the like as a surface hardening treatment to avoid surface damage. However, when coating with these UV curable resins, the resin is charged due to friction with the air while the disk is rotating, and there are many dirt and dust on the read surface due to the adhesion of dust. There is a problem that reduces reliability.
また、 このハードコート層の形成は、 光ディスクでは その信頼性面からホコリなどの異物の付着、 混入を極端 に嫌うために、 クリーンルーム内で行われる。 このよう な制約の下では、 溶媒の使用及び高温の使用は好ましく ない。  In addition, the formation of the hard coat layer is performed in a clean room because the optical disc is extremely unlikely to adhere or mix foreign matter such as dust in terms of reliability. Under these constraints, the use of solvents and high temperatures is not preferred.
本発明は、 かかる現状に鑑みなされたもので、 耐久性 に優れた帯電防止性を有し、 しかも、 十分な表面硬度を 有する光ディスクの提洪を目的とする。 さらに詳しくは 表面電気抵抗が低くかつ表面硬度の高いハードコ一ト層 を基板上に設けた光ディスクの提洪を目的とする。 また 塗工性の観点から無溶媒でも薄膜塗工が可能な低粘度の 硬化性樹脂組成物から形成できるハードコ一卜層を有す る光ディスクを目的とする。 発明の開示  The present invention has been made in view of such circumstances, and has as its object to provide an optical disk having an antistatic property with excellent durability and a sufficient surface hardness. More specifically, an object of the present invention is to provide an optical disk having a hard coat layer having a low surface electric resistance and a high surface hardness provided on a substrate. Another object of the present invention is to provide an optical disc having a hard coat layer that can be formed from a low-viscosity curable resin composition that can be applied as a thin film without using a solvent from the viewpoint of coatability. Disclosure of the invention
本発明者らは、 前記目的、 特に塗工性の観点から無溶 媒でも薄膜塗工が可能な低粘度の硬化性樹脂組成物に着 目して鋭意検討の結果、 特定のモノ （メタ〉 ァクリレー 卜モノマーを含む硬化性組成物が表面硬度に優れ、 かつ 表面電気抵抗も低く出来る事を見いだし、 本発明に到達 した。 The present inventors have developed a low-viscosity curable resin composition which can be applied as a thin film even in a solvent-free manner from the above-mentioned objects, particularly from the viewpoint of coatability. As a result of intensive studies, it has been found that a curable composition containing a specific mono (meth) acrylate monomer has excellent surface hardness and low surface electric resistance, and has reached the present invention.
即ち、 本発明は、 以下の通り第 1発明の特定のモノ That is, the present invention provides the following specific items of the first invention.
(メタ〉 アクリル酸エステルのハードコート層を基本と し、 これから誘導された組成物のハ一ドコート層の 2発 明を含む 3発明からなるものである。 (Meth) The present invention is based on a hard coat layer of an acrylic ester and comprises three inventions including two inventions of a hard coat layer of a composition derived therefrom.
すなわち、 第 1発明は、 少なくとも光照射面 （読み取 り面〉 にハードコート層を形成した光ディスクにおいて、 該ハ一ドコート層が次式 （ェ ）  That is, the first invention provides an optical disc having a hard coat layer formed on at least a light irradiation surface (read surface), wherein the hard coat layer has the following formula (e):
R 1 R2 R 1 R 2
CH2 =C-C0 ( 0CH2 CH ) n OH … （ I 〉 CH 2 = C-C0 (0CH 2 CH) n OH… (I>
〔式中、 R 1 ， R 2 は水素原子またはメチル基を、 nは 1〜2 3の整数を示す。 〕 [In the formula, R 1 and R 2 represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 23. ]
で表されるポリエチレングリコールまたはポリプロピレ ングリコールのモノ （メタ） アクリル酸エステルの少な くとも 1種を含有する硬化性樹脂組成物を硬化してなる 帯電防止性の塗膜であることを特徴とする光ディスクで おる。 Characterized in that it is an antistatic coating film obtained by curing a curable resin composition containing at least one mono (meth) acrylate of polyethylene glycol or polypropylene glycol represented by the formula: It is an optical disk.
第 2発明は、 第 1発明と同じ構成の光ディスクにおい て、 該ハ一ドコート層が次式 （ Π )
Figure imgf000006_0001
A second invention provides an optical disc having the same configuration as the first invention, wherein the hard coat layer has the following formula (層):
Figure imgf000006_0001
CH2 =C-C0 (0CH2 CH) n OR3 … （ H〉 CH 2 = C-C0 (0CH 2 CH) n OR 3 … (H>
〔式中、 R1 ， R2 は水素原子またはメチル基を、 R3 は炭素数 1〜9のアルキル基、 フヱニル基、 炭素数 1〜 9のアルキル基で置換されたフヱニル基、 炭素数 1〜9 のアルコキシ基で置換されたフヱニル基を、 n [Wherein R 1 and R 2 represent a hydrogen atom or a methyl group, R 3 represents an alkyl group having 1 to 9 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 9 carbon atoms, A phenyl group substituted with an alkoxy group of
23の整数を示す。 〕  Indicates an integer of 23. ]
で表されるポリエチレングリコ一ルまたはポリアロピレ ングリコールのモノ （メタ〉 アクリル酸エステルのエー テル誘導体の少なくとも 1種を 5〜70重量％含有する 硬化性樹脂組成物を硬化してなる帯電防止性の塗膜であ ることを特徴とする光ディスクである。 The antistatic properties obtained by curing a curable resin composition containing 5 to 70% by weight of at least one kind of a mono (meth) acrylate derivative of a polyethylene glycol or a polyallopyrene glycol represented by the following formula: An optical disc characterized by being a coating film.
第 3発明は、 同じく第 1発明と同じ構成の光ディスク において、 該ハードコート層が次式 （ Μ ) ft1 R2 The third invention also provides an optical disc having the same configuration as the first invention, wherein the hard coat layer has the following formula (Μ) ft 1 R 2
[CH2 =C-C0 (OCH2 CH)n ] m 0P(0H}3-m ·■· { ! ) [CH 2 = C-C0 (OCH2 CH) n ] m 0P (0H) 3 - m
〔式中、 R1 ， R2 は水素原子またはメチル基を、 nは 1〜23の整数、 mは 1または 2の整数を示す。 〕 で表されるポリエチレングリコ一ルまたはポリプロピレ ングリコールのモノ （メタ〉 アクリル酸エステルのモノ ジ燐酸エステル化合物を 0. 1〜60重量％含有する硬 化性樹脂組成物を硬化してなる帯電防止性の塗膜である ことを特徴とする光ディスクである。 [Wherein, R 1 and R 2 represent a hydrogen atom or a methyl group, n represents an integer of 1 to 23, and m represents an integer of 1 or 2. An antistatic composition obtained by curing a curable resin composition containing 0.1 to 60% by weight of a mono (meth) acrylate monodiphosphate compound of polyethylene glycol or polypropylene glycol represented by the following formula: Is a paint film An optical disc characterized by the above-mentioned.
以下、 本発明の詳細を説明する。  Hereinafter, details of the present invention will be described.
本発明の光ディスクと しては、 ガラスや樹脂などから なる基板上にピッ トが形成された記録媒体からなるコン パクトディスク 〈 C D ) で周知のピットタイプの光ディ スク、 基板上に熱記録層が形成された記録媒体、 レーザ 一光などの照射によりバブルを形成し、 反射光の変化で レベル変動を検知するバブルタイアの光ディスク、 ある いは基板上に光磁気記録層が形成された記録媒体からな る光磁気デイスクなどが含まれる。  The optical disc of the present invention includes a pit-type optical disc known as a compact disc <CD> composed of a recording medium having pits formed on a substrate made of glass, resin, or the like, and a thermal recording layer formed on the substrate. From a recording medium on which a bubble is formed by irradiating a laser beam, etc., and a bubble-tired optical disk that detects a level change based on a change in reflected light, or a recording medium on which a magneto-optical recording layer is formed on a substrate And other magneto-optical disks.
本発明に於て用いられる基板と しては、 ガラス基板の 他に、 ポリ力一ボネート、 ポリメチルメタクリレート、 アモルファスポリオレフィンなどの有機の樹脂基板が用 いられる。 ，  As the substrate used in the present invention, besides a glass substrate, an organic resin substrate such as polycarbonate, polymethyl methacrylate, or amorphous polyolefin is used. ,
光ディスクの記録面とは、 基板上に記録層が形成され ている面をいう。 記録面の反対面すなわち光照射面 〈読 み取り面） は、 例えば光磁気ディスクにおいてはグルー ブが形成されておらずフラットな面である。  The recording surface of an optical disk is a surface on which a recording layer is formed on a substrate. The surface opposite to the recording surface, that is, the light irradiation surface (read surface) is, for example, a flat surface without a groove formed on a magneto-optical disk.
本発明の第 1発明において、 硬化性樹脂組成物中の式 ( ェ 〉 のポリエチレングリコールまたはポリプロピレン ダリコールのモノ （メタ） ァクリル酸エステル [本発明 において （メタ） アクリル酸エステルは、 アクリル酸ェ ステルおよびメタアクリル酸エステルを表わす。 ] の含 有量は、 必要な帯電防止性を有する範囲であればよい。 後述の陰イオン系界面活性剤などを含まず、 式 （ I ) の ポリエチレングリコールまたはポリプロピレングリコ一 ルのモノ （メタ〉 アクリル酸エステルのみで帯電防止性 を付与する場合の前記含有量は 5〜7 0重量％が好まし く、 さらに好ましくは 2 0〜4◦重量％である。 5重量 %未満では帯電防止効果が不足し、 一方 7 0重量％を超 えると該組成物で被覆し硬化させた光ディスクの表面硬 度が不十分で好ましくない。 In the first invention of the present invention, in the curable resin composition, a mono (meth) acrylic acid ester of polyethylene glycol or polypropylene dalicol of the formula (E) [In the present invention, the (meth) acrylic acid ester is an acrylic acid ester and Represents a methacrylic acid ester] as long as it has a necessary antistatic property. The content when the antistatic property is imparted only with a mono (meth) acrylate of polyethylene glycol or polypropylene glycol of the formula (I) without containing an anionic surfactant or the like described below is 5 to 7 0% by weight is preferred, and more preferably 20 to 4% by weight, and if less than 5% by weight, the antistatic effect is insufficient, while if more than 70% by weight, the composition is coated and cured. The surface hardness of the resulting optical disc is insufficient, which is not preferable.
前記の通り、 式 （ ェ ） の R 1 、 R 2 は水素原子又はメ チル基であり、 その U V硬化性、 併用する樹脂との相溶 性および硬化物の表面電気抵抗、 表面硬度を勘案して選 ばれる。 nは 1〜2 3の整数であり、 4〜6が好ましい. この範囲の （メタ〉 ァクリレートが最も高い相溶性を示 し、 かつ低い表面電気抵抗を示す塗膜を与える。 具体的 には、 2—ヒ ドロキシェチルァクリレート、 2—ヒドロ キシェチルメタァクリレート、 ジエチレングリコールモ ノアクリレ一ト、.ジエチレングリコールモノメタァクリ レート、 トリエチレングリコールモノアクリレート、 ト リエチレングリコールモノメタァクリレート、 テトラエ チレングリコールモノメタァクリレート、 ペンタエチレ ングリコールモノメタァクリレート、 へキサエチレング し コ一ルモノメタァクリレート、 テトラエチレングリコ ールモノアクリレート、 ペンタエチレングリコールモノ ァク リレート、 へキサエチレングリコ一ルモノアク リレ ート等が好適に用いられる。 As described above, R 1 and R 2 in the formula (e) are a hydrogen atom or a methyl group, taking into account their UV curability, compatibility with the resin used in combination, and the surface electrical resistance and surface hardness of the cured product. Is chosen. n is an integer of 1 to 23, preferably 4 to 6. A (meth) acrylate in this range has the highest compatibility and gives a coating film having a low surface electric resistance. 2-hydroxyhexyl acrylate, 2-hydroxy methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, triethylene glycol monomethacrylate, Tetraethylene glycol monomethacrylate, pentaethylene glycol monomethacrylate, hexaethylene glycol monomethacrylate, tetraethylene glycol monoacrylate, pentaethylene glycol monoacrylate, hexaethylene glycol monoacrylate Lily Or the like is preferably used.
第 2発明において、 硬化性樹脂組成物中の式 （ H 〉 で 表されるポリエチレングリコ一ルまたはポリプロピレン グリコールのモノ （メタ） アクリル酸エステルのェ一テ ル誘導体の含有量は、 5〜7 0重量％、 好ましくは 1 0 〜6 0重量％、，特に好ましくは 1 5〜5 0重量％である , 該化合物が 5重量％未満では帯電防止効果が不足し、 一 方 7 0重量％を超えると硬化性樹脂組成物で被覆した光 ディスクの表面硬度が不十分で好ましくない。  In the second invention, the content of the ether derivative of the mono (meth) acrylate of polyethylene glycol or polypropylene glycol represented by the formula (H) in the curable resin composition is 5 to 70. % By weight, preferably from 10 to 60% by weight, particularly preferably from 15 to 50% by weight. When the compound is less than 5% by weight, the antistatic effect is insufficient, and on the other hand, it exceeds 70% by weight. And the surface hardness of the optical disk coated with the curable resin composition is insufficient, which is not preferable.
また、 式 （ E ) 中、 nは 5〜2 3の整数である。 この 中で、 nはら〜 2 0が好ましい。 アルキレングリコール 単位を示す nが 5未満であるとダリコール残基の親水性 が低く充分な除電性を示さない。 また、 nが 2 3を超え ると溶解性が低下するので好ましくない。  In the formula (E), n is an integer of 5 to 23. Among them, n is preferably from 20 to 20. If n, which represents an alkylene glycol unit, is less than 5, the dalicol residue has low hydrophilicity and does not exhibit sufficient static elimination properties. On the other hand, if n exceeds 23, the solubility decreases, which is not preferable.
式 （ I〉 中、 R 1 ， R 2 は水素原子またはメチル基を、 R 3 は炭素数 1〜9のアルキル基、 フ ニル基、 炭素数In the formula (I), R 1 and R 2 represent a hydrogen atom or a methyl group, and R 3 represents an alkyl group having 1 to 9 carbon atoms, a phenyl group, and a carbon number.
1〜9のアルキル基で置換されたフ ニル基、 炭素数 1 〜 9のアルコキシ基で置換されたフ 二ル基を示す。 A phenyl group substituted with an alkyl group having 1 to 9 carbon atoms; and a phenyl group substituted with an alkoxy group having 1 to 9 carbon atoms.
R 3 中の炭素数 1〜9のアルキル基と しては、 例えば メチル、 ェチル、 プロピル、 ブチル、 ペンチル、 へキシ ル、 ォクチル基などが挙げられ、 これらは枝分かれして いてもよい。 これらの中で炭素数 1〜4のメチル、 ェチ ル、 プロピル、 ブチル基が好適である。 また、 炭素数 1 〜9のアルキル基で置換されたフヱニル基と しては、 ノ 二ルフヱニル、 ブチルフヱニル、 メチルフエニルなどが 挙げられる。 Examples of the alkyl group having 1 to 9 carbon atoms in R 3 include a methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl group and the like, which may be branched. Of these, a methyl, ethyl, propyl, or butyl group having 1 to 4 carbon atoms is preferred. Further, a phenyl group substituted with an alkyl group having 1 to 9 carbon atoms includes: Examples include diphenyl, butylphenyl, methylphenyl and the like.
式 （ E〉 で表されるポリエチレンダリコールまたはポ リプロピレングリコールのモノ （メタ） ァクリル酸エス テルのェ一テル誘導体としては、 例えば、  Examples of the ether derivative of the mono (meth) acrylate ester of polyethylene daricol or polypropylene glycol represented by the formula (E) include:
CH3 CH 3
CH2 = C-CO(OCH2 CH2 ) OCH: CH 2 = C-CO (OCH 2 CH 2 ) OCH:
CH3 CH 3
CH2 = C-C0(0CH2 CH2 ) a 0C2 H5 CH 2 = C-C0 (0CH 2 CH 2 ) a 0C 2 H 5
CH2 =CHC0 (0CH2 CH2 ) a OCH3 CH 2 = CHC0 (0CH 2 CH 2 ) a OCH3
CH2 =CHC0 {0CH2 CH2 ) a 0C2 H5 CH3 CH 2 = CHC0 (0CH 2 CH 2 ) a 0C 2 H 5 CH 3
CH2 = C-C0(0CH2 CH2 ) n OPI1C9 Hi9 CH 2 = C-C0 (0CH 2 CH 2 ) n OPI1C9 Hi9
CH3 CH 3
CH2 =CHC0 (OCH2 CH) 0PhC4 H, CH 2 = CHC0 (OCH2 CH) 0PhC 4 H,
〔式中、 nは 5〜23、 Pliは p-フヱニレン基を表す〕 [In the formula, n represents 5 to 23, and Pli represents a p-phenylene group.]
などが挙げられる。 And the like.
更に、 具体的には、 CH3 More specifically, CH 3
CH2 = C-CO(OCH2 CH2 ) 9 OC H3 CH3 CH 2 = C-CO (OCH 2 CH 2 ) 9 OC H 3 CH 3
CH2 = C-CO(OCH2 CH 2 ) 23 OC H3 CH 2 = C-CO (OCH 2 CH 2) 23 OC H 3
CH2 =CHCO (OCH2 CH2 ) 9 OC H: CH 2 = CHCO (OCH 2 CH 2 ) 9 OC H :
CH3 CH 3
CH2 = C-CO(OCH2 CH2 ) 8 OPI1C9 H19 などが挙げられるが、 この限りでない。 CH 2 = C-CO (OCH 2 CH 2 ) 8 OPI1C9 H19, but not limited thereto.
第 3発明において、 硬化性樹脂組成物中の式 （ M ) で 表されるポリエチレングリコールまたはポリァロピレン グリコールのモノ （メタ〉 アクリル酸エステル化合物の モノ、 ジ燐酸エステル化合物の含有量は、 0. 1〜6 〇 重量％が好ましく、 更に好ましくは 0. 2〜5 0重量 特に好ましくは 0. 5〜 5 0重量％である。 該化合物が 0. 1重量％未満では帯電防止効果が不足し、 一方 b 〇 重量％を超えると被覆した光ディスクの表面硬度が不十 分で好ましくない。  In the third invention, the content of the mono (meth) acrylate compound of the polyethylene (glycol) or polypropylene glycol represented by the formula (M) in the curable resin composition is 0.1 to 0.1%. The amount is preferably 6% by weight, more preferably 0.2 to 50% by weight, and particularly preferably 0.5 to 50% by weight.と If the content exceeds 10% by weight, the surface hardness of the coated optical disk is insufficient, which is not preferable.
前記の通り、 式 （ Π ) 中、 R1 , ^.2 は水素原子また はメチル基、 nは 1〜23の整数、 mは 1または 2の整 数である。 この中で、 nは 1〜 1 5が好ましく、 1〜 1 〇特に好ましい。 As described above, in the formula ([pi), R 1, ^. 2 is also hydrogen atom a methyl group, n represents an integer of 1 to 23, m is an integer of 1 or 2. Among these, n is preferably 1 to 15 and particularly preferably 1 to 1.
式 （ 21〉 で表されるポリエチレンダリコールまたはポ リプロピレングリコ一ルのモノ 〈メタ〉 ァクリル酸エス テル化合物のモノまたはジ燐酸エステル化合物として 例えば、 Mono <meth> acrylic acid ester of polyethylene dalicol or polypropylene glycol represented by the formula (21) As a mono- or diphosphate compound of a ter compound, for example,
CH3 CH 3
CH2 = C-C0(0CH2 CH2 ) a 0P(0H)2 CH 2 = C-C0 (0CH 2 CH 2 ) a 0P (0H) 2
CH2 =CH-C0(0CH2 CH2 ) a 0P(0H)2 CH 2 = CH-C0 (0CH 2 CH 2 ) a 0P (0H) 2
CH3 CH3 CH 3 CH 3
CH2 = -C0(0CH2 CH) n 0P(0H}2 CH 2 = -C0 (0CH 2 CH) n 0P (0H) 2
CH3 CH 3
CH2 =CH-C0(0CH2 CH) a 0P(0H)2 CH3 CH 2 = CH-C0 (0CH 2 CH) a 0P (0H) 2 CH 3
[ CH2 = C-C0{0CH2 CH2 ) a 0]2 POH [CH 2 = C-C0 {0CH 2 CH 2 ) a 0] 2 POH
CH3 CH3 CH 3 CH 3
[ CH2 = C-C0{0CH2 CH) a 0]2 POH [CH 2 = C-C0 {0CH 2 CH) a 0] 2 POH
CH3 CH 3
「CH2 =CH-C0(0CH2 CH) a 0] 2 POH [CH2 =C-C0 (OCH2 CH2 ) n 0] 2 POH “CH 2 = CH-C0 (0CH 2 CH) a 0] 2 POH [CH 2 = C-C0 (OCH2 CH 2 ) n 0] 2 POH
[ただし、 式中、 nは.1〜23の整数を表す] などが挙げられる。 [Wherein, n represents an integer of from 0.1 to 23].
さらに具体的には  More specifically,
CH = CH-C00CH2 CH2 OP (OH) 2 CH = CH-C00CH 2 CH2 OP (OH) 2
(ライ トエステル DM、 兵栄社油脂㈱製） CH: (Light ester DM, Hyoeisha Yushi Co., Ltd.) CH:
CH2 = C - COOCH2 CH2 OP(OH}2 CH 2 = C-COOCH 2 CH 2 OP (OH) 2
(ホスマー M、 ュニケミカル糨製）  (Hosmer M, manufactured by Unichemical Co., Ltd.)
CH3 CH3 CH 3 CH 3
CH2 = C- C00CH2 CH0P(0H}2 CH 2 = C- C00CH 2 CH0P (0H) 2
(ホスマ一 P、 ュニケミカル㈱製〉  (Hosma-P, manufactured by Unichemical Co., Ltd.)
CH3 CH 3
CH2 = C-C0(0CH2 CH2 ) 5- 6 0P(0H)2 CH 2 = C-C0 (0CH 2 CH 2 ) 5-6 0P (0H) 2
(ホスマー P E、 ュニケミカル㈱製  (Hosmer PE, manufactured by Unichemical Co., Ltd.
CH: CH: CH: CH:
CH2 = C-C0(0CH2 CH) 5-6 0P(0H)2 CH 2 = C-C0 (0CH 2 CH) 5 -6 0P (0H) 2
(ホスマー P P、 ュニケミカル㈱製〉  (Hosmer PP, manufactured by Unichemical Co., Ltd.)
CH3 CH 3
「CH2 = C- C00CH2 CH2 0]n P(0H) s-n ( n = 1 , 2 ( RW- 1 1 6 2 H P、 日本乳化剤㈱製） などが挙げられる。 なお上式の括弧内はその市販の商品 名とメーカ一名である。 以下同様である。 "CH 2 = C-C00CH 2 CH 2 0] n P (0H) sn (n = 1, 2 (RW-116 hp, manufactured by Nippon Emulsifier Co., Ltd.). The commercial product name and the manufacturer are the same.
この第 3発明において、 前記燐酸エステル化合物を式 ( Π/ ) のエチレングリコールモノ （メタ〉 ァクリル酸ェ ステルの燐酸モノエステル化合物と し、 これと有機アミ ン化合物の 1 ： 1付加物と して硬化性樹脂組成物に含有 せしめることにより、 帯電防止性能を、 引いては表面硬 度を向上できる。 この付加物の硬化性樹脂組成物中の舍 有量は、 0. 1〜'20重量％、 好ましくは 0. 2〜1 5 重量％、 特に好ましくは 0. 5〜10重量％でぁる。 該 付加物が 0. 1重量％未満では帯電防止効果が不足し、 一方 20重量％を超えると硬化性樹脂とに相溶しにくく なり、 塗膜の形成性の観点から好ましくない。 In the third invention, the phosphoric ester compound is an ethylene glycol mono (meth) acrylic acid ester phosphoric acid monoester compound of the formula (Π /), which is a 1: 1 adduct of an organic amine compound. Contained in curable resin composition By doing so, the antistatic performance and, consequently, the surface hardness can be improved. The content of the adduct in the curable resin composition is from 0.1 to '20% by weight, preferably from 0.2 to 15% by weight, particularly preferably from 0.5 to 10% by weight. If the amount of the adduct is less than 0.1% by weight, the antistatic effect is insufficient, while if it exceeds 20% by weight, it becomes difficult to be compatible with the curable resin, which is not preferable from the viewpoint of coatability.
このエチレングリコールモノ （メタ〉 アクリル酸エス テルの燐酸モノエステル化合物と有機アミン化合物の 1 1付加物としては、 例えば、  As the 11-adduct of a phosphoric acid monoester compound of ethylene glycol mono (meth) acrylate and an organic amine compound, for example,
CH3 CH 3
CH2 = C- C00CH2 CH2 OP (OH) 2 / CH 2 = C- C00CH 2 CH 2 OP (OH) 2 /
CH3 CH 3
CH2 = C- COOCH2 CH2 N(CH 3 ) 2 CH 2 = C- COOCH2 CH 2 N (CH 3) 2
CH3 CH 3
CH2 = C- COOCH2 CH2 OP (OH) 2 / CH 2 = C- COOCH2 CH 2 OP (OH) 2 /
CH3 CH 3
CH2 = C- C00CH2 CH2 N (C2 H5 ) 2 CH 2 = C- C00CH 2 CH 2 N (C 2 H 5 ) 2
CH3 CH 3
CH2 = C- COOCH2 CH2 0P(0H)2 / H2 N CH2 CH2 OH CH3 CH 2 = C- COOCH2 CH 2 0P (0H) 2 / H 2 N CH 2 CH 2 OH CH 3
CH2 = C- COOCH2 CH2 0P{0H}2 Z(C2 H5 ) 3 N などが挙げられる。 CH 2 = C- COOCH2 CH 2 0P {0H} 2 Z (C 2 H 5 ) 3 N And the like.
以上の本発明において、 硬化性樹脂組成物の前記式 In the above invention, the above formula of the curable resin composition
(ェ ） 〜 （！ V ) の化合物以外の成分には、 一般に知られ た重合性単量体や重合性オリゴマー、 重合性ァレポリマ —が用いられる。 例えばビスフヱ ノール Aエポキシァク リレート、 脂肪酸変性エポキシァクリレ一ト、 ノボラッ クエポキシァクリレート、 フヱノールノボラックェポキ シァクリレート、 ポリエステルオリゴウレタンァクリレ —ト、 多官能ヒドロキシ化合物のウレタンァクリレ一ト、 ポリブタジエンァクリレート、 ペンタエリスリ トールテ トラ （メタ〉 ァクリレート、 ジペンタエリスリ トールへ キサ （メタ） ァクリレート、 トリメチ口一ルァロパン卜 リ （メタ） ァクリレート、 （ポリ〉 アルキレングリコ一 ルのジ （メタ〉 ァクリレートなどの脂肪族多官能ァクリ レ一ト、 多官能オリゴエステルァクリレート、 多官能ポ リエステルァクリレ一ト、 ホスファゼン化合物のァクリ レート変性物、 イソシァヌル酸の多官能ァクリレート、 その他ビニル重合性化合物、 アクリル系重合性化合物な どが使用できる。 これらの重合性化合物は単独あるいは 混合して使用される。 As the components other than the compounds (d) to (! V), generally known polymerizable monomers, polymerizable oligomers, and polymerizable copolymers are used. For example, bisphenol A epoxy acrylate, fatty acid modified epoxy acrylate, novolak epoxy acrylate, phenol novolak epoxy acrylate, polyester oligo urethane acrylate, polyfunctional hydroxy compound urethane acrylate, polybutadiene acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethyl acrylate (meth) acrylate, (poly) alkylene glycol di (meth) acrylate and other aliphatic polyfunctional acrylates. Multifunctional oligoester acrylate, polyfunctional polyacrylate, acrylate modified phosphazene compound, polyfunctional acrylate of isocyanuric acid, etc. Use may be made of vinyl polymerizable compounds, acrylic polymerizable compounds, etc. These polymerizable compounds may be used alone or as a mixture.
本発明の硬化性樹脂組成物は、 必要に応じて、 光重合 開始剤、 熱重合開始剤などのラジカル重合開始剤などを 添加して用いる。  The curable resin composition of the present invention is used by adding a radical polymerization initiator such as a photopolymerization initiator and a thermal polymerization initiator, if necessary.
本発明、 特にその第 1発明において、 帯電防止性能及 び表面硬度の両面、 更には膜形成性の面より下記組成の 硬化性樹脂組成物が好ましい。 In the present invention, particularly in the first invention, the antistatic performance and A curable resin composition having the following composition is preferred from the viewpoint of both surface hardness and surface hardness, and further from the viewpoint of film forming properties.
すなわち、 前記式 （ I ) の （メタ） ァクリル酸エステ ルとしては nが 4〜 6のものとし、 硬化性樹脂組成物の これ以外の成分としては、 ジペンタエリスリ 卜一ルへキ サァクリレートまたはその力アロラクトン変性体、 必要 に応じてこれら以外の重合性希釈剤、 及び重合開始剤か らなる硬化性樹脂組成物である。  That is, the (meth) acrylic acid ester of the formula (I) has n of 4 to 6, and the other components of the curable resin composition include dipentaerythritol hexaacrylate or its allolactone. It is a curable resin composition comprising a modified product, if necessary, a polymerizable diluent other than these, and a polymerization initiator.
ジペンタエリスリ トールへキサァクリレートまたはそ の力アロラクトン変性体は、 比較的粘土が低く、 硬化性 が高い点で好適であり、 この中では力アロラクトン変性 体がより好ましい。 力アロラクトン変性体は、 下式で表 わされる。  Dipentaerythritol hexacrylate or its modified allolactone is suitable in that it has relatively low clay and high curability, and among these, the modified allolactone is more preferable. The modified force allolactone is represented by the following formula.
A-[0(CH2 ) 5 CO] p -0CH; CH20-[C0(CH2 ) 50] s -A A- [0 (CH 2) 5 CO] p -0CH; CH 2 0- [C0 (CH 2) 5 0] s -A
/  /
Λ- [0 (CH2 ) 5 CO] q -0CH2 -CCH2 OC H2 C-CH20- [CO (CH2 ) 50]t -A A- [0 (CH2 ) 5 CO] r -OCH2 CH20- [CO {CH2 ) 5 0]u -A Λ- [0 (CH 2) 5 CO] q -0CH 2 -CCH 2 OC H 2 C-CH 2 0- [CO (CH 2) 50] t -A A- [0 (CH 2) 5 CO] r -OCH2 CH 2 0- [CO (CH 2 ) 5 0] u -A
「式中、 Aは C H2 =CHC O—であり、 p、 q、 r、 s、 tおよび uは 0〜1 0の整数であり、 かつ、 p + q + r + s + t + u 14である。 」 Wherein A is CH 2 = CHC O—, p, q, r, s, t and u are integers from 0 to 10 and p + q + r + s + t + u 14 It is. "
一般にはジペンタエリスリ トールと力アロラクトンお よびァクリル酸を直接あるいは逐次的にエステル化する ために、 これらの化合物の混合物として得られる。 また 力アロラク トン変性の程度はジペンタエリスリ トールに 対する力アロラク トンの使用量で決まる。 P + q + r + s + t + u≥ 1 5では、 光架橋性のァクリレー卜基の密 度が低下するため架橋密度が低下し、 目的とする硬度が 発現せず、 好ましくない。 Generally, it is obtained as a mixture of dipentaerythritol and these compounds in order to directly or sequentially esterify the allolactone and acrylic acid. Also The degree of force allolactone modification is determined by the amount of force allolactone used for dipentaerythritol. In the case of P + q + r + s + t + u ≥ 15, the density of the photocrosslinkable acrylate group is reduced, so that the crosslink density is reduced and the desired hardness is not exhibited, which is not preferable.
具体的には日本化薬㈱製の商品名 D P C A 2◦、 D P Specifically, Nippon Kayaku Co., Ltd. product names D P C A 2◦, D P
C A 3 0、 D P C A 6 0、 D P C A 1 2 0が挙げられる。 これらはジペンタエリスリ トールをそれぞれ平均 2、 3、 6、 1 2分子の力プロラクトンで変性したものであり、 皮膚刺激性が少なく、 臭気が少ないモノマーで、 硬化速 度は極めて早く、 且つ硬化物は硬度が高いにも拘らず柔 軟性を示すため、 耐候性に優れた硬化物を与える。 更に、 粘度も低いため組成物を形成したときに塗布性も良好と なる。 CA30, DPCA60, and DPCA120. These are dipentaerythritols modified with 2, 3, 6, and 12 molecules of force prolactone, respectively, on average, and have low skin irritation and low odor.The curing speed is extremely fast, and the cured product is Since it shows flexibility despite its high hardness, it gives cured products with excellent weather resistance. Furthermore, since the viscosity is low, the coatability is good when the composition is formed.
硬化性樹脂組成物中のこの成分の含有量は、 4 0〜 8〇重量％、 好適には 5 0〜8 0重量％である。 それ以 上では、 塗膜の表面電気抵抗が高くなり好ましくない。 また、 それ以下では、 塗膜の表面硬度を上げることが出 来ないため好ましくない。  The content of this component in the curable resin composition is 40 to 80% by weight, preferably 50 to 80% by weight. Above this, the surface electric resistance of the coating film is undesirably high. In addition, if it is lower than that, it is not preferable because the surface hardness of the coating film cannot be increased.
重合性希釈剤は、 硬化性樹脂組成物の塗工の際の粘度 を下げる目的で必要に応じて用いられる。 従って、 それ 自体低粘度の 1〜3官能性の 〈メタ） ァクリレートなど が用いられる。 併用する成分 〈 a ) の前記 （メタ） ァク リル酸エステルおよび成分 （ b ) の前記ジペンタエリス リ ト一ル （メタ〉 ァクリレートの種類と組成にもよるがThe polymerizable diluent is used as needed for the purpose of lowering the viscosity at the time of applying the curable resin composition. Therefore, low-viscosity (meth) acrylates having 1 to 3 functionality are used. Component (a) the (meth) acrylate and component (b) the dipentaerythr Retile (meta) Depends on the type and composition of acrylate
13型粘度計をによる 2 5 Cの測定で粘度 1 0ボイズ以下 好ましくは 5ポィズ以下の （メタ〉 ァクリレートが用い ちれる。 A (meth) acrylate having a viscosity of 10 vise or less, preferably 5 poise or less, at 25 C measured by a 13-type viscometer is used.
好適に用いられる （メタ） ァクリレートと しては、 へ キサメチレングリコールジァクリレート、 テトラヒドロ フルフリルァクリレート、 へキサメチレングリコールジ メタァクリレート、 テトラヒドロフルフリルメタァクリ レート、 トリメチ口一ルァロパントリアクリレ一ト、 ヒ ドロキシピバリン酸ネオペンチルグリコールジァクリレ ート、 グリセ口一ルジメタァクリレート、 ネオペンチル グリコ一ルジァクリレ一ト、 ネオペンチルグリコールジ メタァクリレート、 ペンタエリスリ トールテトラァクリ レートが好適に用いられる。 これらの中でへキサメチレ ングリコールジァクリレ一ト、 テトラヒドロフリルァク リレー卜が硬化物のポリカーボネート基板への接着性を 改良したり、 組成物の粘度を調製する上で特に好適に用 いられる。  As the (meth) acrylate preferably used, hexamethylene glycol diacrylate, tetrahydrofurfuryl acrylate, hexamethylene glycol dimethacrylate, tetrahydrofurfuryl methacrylate, and trimethylethyl-1-fluoropropria Preferably used are acrylate, neopentyl glycol hydroxypivalate, glyceryl dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, and pentaerythritol tetraacrylate. Can be Of these, hexamethylene glycol diacrylate and tetrahydrofuryl acrylate are particularly suitably used for improving the adhesion of the cured product to the polycarbonate substrate and adjusting the viscosity of the composition. Can be
この成分 （ c ) の重合性希釈剤の使用量は、 使用しな い場合を含めて硬化性樹脂組成物の 0〜4 0重量％、 好 ましくは 0〜3 0重量％である。 それ以上では、 種類に よっては表面硬度が高くなるが、 表面電気抵抗が低下せ ず、 また基板との接着性が低下するために好ましくない 重合開始剤は、 上述の成分 （ a ) の （メタ） アクリル 酸エステル、 成分 （ b ) のジペンタエリスリ ト一ル （メ タ〉 ァクリレート、 及び成分 （ C ) の重合性希釈剤の合 計量に対して 0. l〜 1 0phr (weight .part per hundred resin ) 、 好ましくは 0. 5〜7phr 、 更に好 ましくは 2〜5phr が用いられる。 The amount of the polymerizable diluent used as the component (c) is 0 to 40% by weight, preferably 0 to 30% by weight of the curable resin composition including the case where it is not used. Above that, the surface hardness increases depending on the type, but the surface electric resistance does not decrease and the adhesion to the substrate is deteriorated. Thus, the polymerization initiator is not preferable. Acrylic The acid ester, the dipentaerythritol (meta) acrylate of the component (b), and the polymerizable diluent of the component (C) are preferably 0.1 to 10 phr (weight.part per hundred resin) based on the total weight. Is 0.5 to 7 phr, more preferably 2 to 5 phr.
光重合開始剤と しては、 ベンゾフヱノン、 ミヒラ一ズ ケトンなどのベンゾフヱノン系開始剤、 ベンジル、 フエ ニルメ トキシジケトンなどのジケトン系開始剤、 ァセト フエノンなどのァセトフヱノン系開始剤、 ベンゾインェ チルェ一テル、 ベンジルジメチ/レケタ一/レなどのべンゾ イン系開始剤、 2, 4-ジェチルチオキサントンなどのチォ キサントン系開始剤、 2—メチルアントラキノン、 カン ファーキノンなどのキノン系開始剤などが好適に用いら れる。 必要に応じてアミン系促進剤などの促進剤の併用 も可能である。  Examples of the photopolymerization initiator include benzophenone-based initiators such as benzophenone and Michler's ketone; diketone-based initiators such as benzyl and phenylmethoxydiketone; acetphenone-based initiators such as acetophenone; benzoinethyl ether and benzyldimethine. Benzoin-based initiators such as / reketane / re, thioxanthone-based initiators such as 2,4-getylthioxanthone, and quinone-based initiators such as 2-methylanthraquinone and camphorquinone are preferably used. . If necessary, an accelerator such as an amine accelerator can be used in combination.
また、 熱硬化の場合の重合開始剤としては、 ァゾビス ィスブチロニトリル 〈 A I B N〉 、 ベンゾィルペルォキ シド （ B P O ) 、 クメンヒドロペルォキシド、 ジクミル ペル才キシド、 ジタ一シャリーブチルペルォキシド、 ラ ゥロイルベルォキシドなどが挙げられる。  In addition, as the polymerization initiator in the case of heat curing, azobisdisbutyronitrile <AIBN>, benzoylperoxide (BPO), cumene hydroperoxide, dicumyl peroxyloxide, dibutyl butylperoxide Oxide, peryl yl beloxide and the like.
以上本発明、 特にその第 1発明の好ましい一態様を説 明した。 更に、 これらに陰イオン系界面活性剤を含有せ しめることにより、 帯電防止性能を向上させることがで きる。 かかる陰イオン系界面活性剤と しては、 飽和ゃ不 飽和の脂肪酸アル力リ金属塩、 飽和や不飽和の脂肪族の スルホン酸塩、 置換基を含んでもよい芳香族のスルホン 酸塩、 エチレングリコール単位を含むスルホン酸塩、 各 種置換基を含むサルフ —トのナトリゥム塩などが挙げ ちれる。 具体的にはトデシルベンゼンスルホン酸ナトリ ゥム、 ァシル （牛脂〉 メチルタウリン酸ナトリウム、 ラ ゥロイルメチルタウリン酸ナトリウム、 《—スルホ脂肪 酸エステルナトリウム塩、 ァシドエーテルナトリウムサ ルフ： !：一ト、 アルキルエーテルスルホン酸ナトリウム、 アルキルサルフヱ一トナトリゥム塩、 アルキルエーテル サルフェートナトリウム塩、 ォレイン酸カリウム、 ヤシ 脂肪酸カリウムなどの脂肪酸石験が挙げられる。 この中 でスルホン酸の塩化合物、 硫酸エステルの塩化合物が好 ましい。 The present invention has been described above, particularly a preferred embodiment of the first invention. Further, by adding an anionic surfactant to these, the antistatic performance can be improved. As such anionic surfactants, saturated and non-saturated Saturated fatty acid metal salts, saturated or unsaturated aliphatic sulfonates, aromatic sulfonates that may have substituents, sulfonates containing ethylene glycol units, and sulfur containing various substituents —Salt sodium salt. Specifically, sodium todecylbenzenesulfonate, acyl (tallow) sodium methyltaurate, sodium radioylmethyltaurate, «-sulfofatty acid sodium salt, sodium acid ether sodium:! And fatty acid tests such as sodium alkyl ether sulfonate, alkyl sulfate sodium salt, sodium alkyl ether sulfate, potassium oleate and potassium coconut fatty acid, among which sulfonic acid salt compounds and sulfate ester salt compounds are preferred. Good.
この陰イオン系界面活性剤の含有量は、 前述した第 1 発明の基本構成に使用する場合には、 成分 （ a ) の式 When used in the basic constitution of the first invention described above, the content of the anionic surfactant is determined by the formula of the component (a).
( I 〉 の （メタ） ァクリル酸エステルの量に対して 0 . 0 1〜2 0 0重量％、 更に好ましくは 0 . 1〜 (I) 0.01 to 200% by weight, more preferably 0.1 to 200% by weight, based on the amount of the (meth) acrylic acid ester in (I).
1 0ひ重量％であり、 前述した第 1発明の好ましい態様 に使用する場合には、 該成分 （ a ) の （メタ） ァクリル 酸エステル、 前述の成分 （ b ) のジペンタエリスリ トー ルおよび成分 （ c ) の重合性希积剤の合計重量に対して 0 . 0◦ 1〜1 0重量％である。 陰イオン系界面活性剤 When used in the above-mentioned preferred embodiment of the first invention, (meth) acrylate of the component (a), dipentaerythritol of the component (b) and the component (c) )) Is 0.0 ° to 1 to 10% by weight based on the total weight of the polymerizable diluent. Anionic surfactant
[成分 （ e ) ] の含有量がこの範囲未満では硬化が不十 分で、 この範囲を越えると溶解性の点から好ましくない < ところで、 この成分 （ e ) の陰イオン系界面活性剤は 成分 （ a〉 の式 （ I 〉 のァクリル酸エステルと相互に働 き硬化物に優れた帯電防止性を付与する。 理由は定かで ないが、 成分 （ a〉 が固体電解質的な役割をして成分If the content of [Component (e)] is less than this range, curing is insufficient. If the amount exceeds this range, it is not preferable from the viewpoint of solubility. By the way, the anionic surfactant of this component (e) interacts with the acrylate of the formula (I) of component (a) to cure. Provides excellent antistatic properties to materials, for unknown reasons, but component (a) acts as a solid electrolyte
( e ) と特殊な相互作用をしているものと推定される。 したがって、 成分 （ e 〉 を用いると、 用いない場合に 比べて帯電防止性が向上するので、 硬化性樹脂組成物中 の成分 （ a ) の含有量は、 この成分 ( e ) を用いない場 合に比べて少なくてよく、 その好ましい範囲は 3〜4 0 重量％である。 該成分 （ a ) は 3重量％未満では成分It is presumed that it has a special interaction with (e). Therefore, when the component (e) is used, the antistatic property is improved as compared with the case where the component (e) is not used. Therefore, the content of the component (a) in the curable resin composition is determined when the component (e) is not used. The preferred range is from 3 to 40% by weight, and the component (a) is less than 3% by weight.
( e ) との相互作用の割合が不十分で帯電防止効果が不 足し、 一方、 成分 （ a ) が 4 0重量％を越えると得られ るハードコート層の表面硬度が不十分となり好ましくな い c The proportion of the interaction with (e) is insufficient and the antistatic effect is insufficient. On the other hand, if the component (a) exceeds 40% by weight, the surface hardness of the obtained hard coat layer is insufficient, which is not preferable. c
以上の本発明の硬化性樹脂組成物は、 公知のスピンコ 一ティング法、 浸漬コーティング法、 ドクターナイフに よるコーティング、 バーコータ一による方法で、 光ディ スクの表面を被覆することが出来る。 特にスピンコーテ ィング法は、 膜厚が容易に制御で実用上最も好ましい。 光ディスクの被覆にあたっては、 光ディスクの側面をも 被覆すると帯電防止効果を向上させることが出来る。 い ずれにせよ溶媒を用いずに塗工を可能にするために、 該 硬化性樹脂組成物の粘度は、 B型粘度計をによる 2 5 C の測定で 2 0ボイズ以下、 好ましくは 1 0ボイズ以下、 更に好ましくは 5ボイズ以下である。 それ以上では塗膜 制御が円滑に行えないために好ましくない。 The curable resin composition of the present invention described above can coat the surface of the optical disc by a known spin coating method, dip coating method, coating with a doctor knife, or a method with a bar coater. In particular, the spin coating method is practically most preferable because the film thickness is easily controlled. When coating the optical disk, covering the side surface of the optical disk also improves the antistatic effect. In any case, in order to enable coating without using a solvent, the viscosity of the curable resin composition is measured at 25 C using a B-type viscometer. Is less than 20 boys, preferably less than 10 boys, more preferably less than 5 boys. Above that, it is not preferable because the coating film cannot be controlled smoothly.
本発明の硬化後の塗膜の厚さは 1〜3 0 mであり、 好ましくは 5〜2 5 mである。 それ以下では硬度の上 で十分な性能が発揮されず、 それ以上では膜厚制御が困 難になるばかりか、 内部の硬化性が低下するために好ま しくない。  The thickness of the cured coating film of the present invention is 1 to 30 m, preferably 5 to 25 m. If it is lower than this, sufficient performance is not exhibited in terms of hardness, and if it is higher than this, not only is it difficult to control the film thickness, but also the internal curability decreases, which is not preferable.
該組成物を塗布した光ディスクは低圧水銀灯、 中圧水 銀灯、 高圧水銀灯などの紫外ランプ、 ハロゲンランプ、 電子線などの活性光線、 あるいは熱処理などを用いて公 知の方法、 条件により硬化される。 この中で、 紫外ラン ァ、 ハロゲンランプ、 電子線などの活性光線を用いるの が操作性、 生産性の観点から好ましい。  The optical disk coated with the composition is cured by known methods and conditions using an active lamp such as an ultraviolet lamp such as a low-pressure mercury lamp, a medium-pressure mercury lamp, and a high-pressure mercury lamp, a halogen lamp, an electron beam, or a heat treatment. . Among them, it is preferable to use actinic rays such as an ultraviolet lamp, a halogen lamp, and an electron beam from the viewpoint of operability and productivity.
本発明での帯電防止性は、 ゴミ、 ホコリなどの異物の 表面への付着がないものであれば良い。 これは具体的に は表面電気抵抗で表示され、 光ディスクでは 1 0 1 5 Ω Ζ □未満、 好ましくは 1 0 1 4 Ω ΖΕ]未満と言われている。 また、 表面硬度は、 通常の取扱い、 具体的には布による 表面清掃、 爪による引つかきなどにより傷の生じない程 度が必要と言われている。 'これは、 具体的には J I S親 格に規定された鉛筆硬度で表示でき、 一般的には H B以 上、 好ましくは F以上である。 本発明では、 これらを判 断基準に用いた。 以上、 本発明は、 高度の耐久性をもつ帯電防止能を有 し、 しかも充分な表面硬度を有する光ディスクを提供す ることができる。 発明を実施するための最良の形態 The antistatic property in the present invention may be any as long as foreign substances such as dust and dust do not adhere to the surface. This is displayed in detail on the surface resistivity, 1 0 1 5 Ω Ζ □ less than the optical disc, preferably it is said that less than 1 0 1 4 Ω ΖΕ]. It is said that the surface hardness must be small enough not to cause scratches due to normal handling, specifically cleaning the surface with a cloth, or catching with a nail. 'Specifically, this can be represented by the pencil hardness specified in JIS standard, and is generally HB or more, preferably F or more. In the present invention, these are used as criteria. As described above, the present invention can provide an optical disc having an antistatic ability with a high degree of durability and a sufficient surface hardness. BEST MODE FOR CARRYING OUT THE INVENTION
本発明をさらに詳細に説述するために、 実施例に従つ てこれを説明する。 なお、 本発明はかかる実施例に限定 されない。  The present invention will be described in further detail with reference to Examples. Note that the present invention is not limited to such an example.
実施例において 表面抵抗 （ 〉 は J I S K In the examples, the surface resistance () is J I S K
6 9 1 1によった また、 鉛筆硬度は、 三菱鉛筆製ュニ を用いて測定した なお、 化合物の後の括弧内は実際に 用いた市販の商品名とそのメーカー名を示す。 The pencil hardness was measured using a Mitsubishi Pencil-made unit. Parentheses after the compound indicate the names of commercial products actually used and the manufacturer's name.
〔実施例 1〜2 1 、 比較例 1， 2〕 [Examples 1-21 and Comparative Examples 1 and 2]
厚さ 1 . 2 mm、 直径 1 3 O Mのポリ力一ボネート基板 のフラッ ト面に硬化性樹脂組成物 （日本精化 製、 N S C - 7 1 0 6 ) と、 下記の各種のモノ （メタ〉 アクリル 酸エステル、 その燐酸エステル、 又はそれと有機アミン 化合物との 1 ： 1付加物の共重合モノマーの夫々との混 合物を約 1 O ^t mの厚さになるようにスピンコート法に より塗布した。 引き続き、 長さ約 2 7 c m、 2 K wの高圧 水銀灯を用い、 2 0 c mの高さから紫外線を 1分閭照射し, 塗膜を硬化させた。 共重合モノマー A curable resin composition (NSC-710, manufactured by Nippon Seika Co., Ltd.) and the following various objects (meta) are placed on the flat surface of a polycarbonate substrate with a thickness of 1.2 mm and a diameter of 13 OM. Acrylic ester, its phosphoric ester, or a mixture of a 1: 1 adduct of it and an organic amine compound with each of the copolymerized monomers is applied by spin coating to a thickness of about 1 O ^ tm. Subsequently, ultraviolet rays were irradiated from a height of 20 cm for 1 minute using a high-pressure mercury lamp of about 27 cm in length and 2 Kw to cure the coating film. Copolymerized monomer
CH3 CH 3
CH2 = C-CO (0CH2 CH2 ) i50H CH 2 = C-CO (0CH 2 CH 2 ) i 5 0H
( MA 1 50 日本乳化剤㈱製）  (MA 150 manufactured by Nippon Emulsifier Co., Ltd.)
CH3 CH 3
CH2 = C-C0(0CH2 CH2 ) 9 OCH3 CH 2 = C-C0 (0CH 2 CH 2 ) 9 OCH3
( MP G- 1 3 0 MA 日本乳化剤㈱製〉  (MP G-130 MA manufactured by Nippon Emulsifier Co., Ltd.)
CH3 CH 3
CH2 = C-C0(0CH2 CH2 ) 8 0PhC9 H19 CH 2 = C-C0 (0CH 2 CH 2 ) 8 0PhC 9 H 19
( RMA- 862 日本乳化剤㈱製）  (RMA-862 manufactured by Nippon Emulsifier Co., Ltd.)
CH2 =CH- COOCH2 CH2 0P(0H}2 CH 2 = CH-COOCH2 CH 2 0P (0H) 2
(ライ トエステル DM 共栄社油脂糨製〉  (Light ester DM manufactured by Kyoeisha Yushi Co., Ltd.)
CH3 CH 3
CH2 = C- C00CH2 CH2 0P(0H)2 CH 2 = C- C00CH 2 CH 2 0P (0H) 2
(ホスマー M ュニケミカル眯製）  (Manufactured by Hosmer M Unichemical Co., Ltd.)
CH3 CH3 CH 3 CH 3
CH2 = C- COOCH2 CH0P(0H)2 CH 2 = C- COOCH2 CH0P (0H) 2
(ホスマー P ュニケミカル㈱製）  (Manufactured by Hosmer P Unichemical Co., Ltd.)
CH3 CH 3
CH2 = C-C0(0CH2 CH2 ) 5-6 0P(0H)2 CH 2 = C-C0 (0CH 2 CH 2 ) 5-6 0P (0H) 2
(ホスマー P E ュニケミカル㈱製） CH3 CH3 (Manufactured by Hosmer PE Unichemical Co., Ltd.) CH 3 CH 3
CH2 = C-C0(0CH2 CH) 5-6 OP(OH)2 CH 2 = C-C0 (0CH 2 CH) 5 -6 OP (OH) 2
(ホスマ一 P P ュニケミカル㈱製〉  (Manufactured by Hosuma P P Unichemical Co., Ltd.)
CH3 CH 3
[ CH2 = C- C00CH2 CH2 0]n P(0H) 3-a ( n = 1 , 2 ) [CH 2 = C- C00CH 2 CH 2 0] n P (0H) 3 -a (n = 1, 2)
( W- 1 1 6 2 H P 日本乳化剤㈱製）  (W-1 1 6 2 H P Nippon Emulsifier Co., Ltd.)
CH3 CH 3
CH2 = C- C00CH2 CH2 0P(0H)2 / CH 2 = C- C00CH 2 CH 2 0P (0H) 2 /
CH3 CH 3
CH2 = C- C00CH2 CH2 N(CH 3 ) 2 CH 2 = C- C00CH 2 CH 2 N (CH 3) 2
(ホスマ一 DM ュニケミカル㈱製〉  (Manufactured by Hosuma DM Unichemical Co., Ltd.)
CH3 CH 3
CH2 = C- C00CH2 CH2 0P(0H}2 / CH 2 = C- C00CH 2 CH 2 0P (0H) 2 /
. CH3 . CH 3
CH2 = C- COOCH2 CH2 N( C2 H5 ) 2 CH 2 = C- COOCH2 CH 2 N (C 2 H 5 ) 2
(ホスマ一 D E ュニケミカル㈱製）  (Manufactured by Hosuma D E Unichemical Co., Ltd.)
CH3 CH 3
CH2 = C- COOCH2 CH2 0P(0H)2 / H2 NCH2 CH2 OH CH 2 = C- COOCH2 CH 2 0P (0H) 2 / H 2 NCH 2 CH 2 OH
(ホスマ一 MH ュニケミカル臃製）  (Manufactured by Hosuma MH Unichemical Co., Ltd.)
比較例 1は前記共重合モノマーを添加しない場合であ り、 比較例 2は、 ポリカーボネート基板上に、 練り込み 型帯電防止剤ソルビタンラウレー卜 （ Newcol 20 , 日 本乳化剤㈱製） をアルコールに溶かして塗布し、 乾燥し たものである。 Comparative Example 1 was a case where the copolymerized monomer was not added, and Comparative Example 2 was a solution in which a kneading-type antistatic agent sorbitan laurate (Newcol 20, manufactured by Nippon Emulsion Co., Ltd.) was dissolved in alcohol on a polycarbonate substrate. And apply, dry It is a thing.
前記硬化条件でこれら塗布物を硬化させた場合、 外見 上、 硬化は充分で残存モノマーを示すベタツキなどは認 められなかった。  When these coated products were cured under the above-mentioned curing conditions, they were sufficiently cured in appearance, and no stickiness indicating residual monomers was observed.
硬化後のポリカーボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
結果を表 1に示す。 Table 1 shows the results.
Figure imgf000027_0001
突施例 1〜 21および比較例 1で得られた光磁気ディ スクを、 室温下に 24時間純水中に浸漬後表面抵抗を測 定したが変化はなかった。 比較例 2の同様処理後の表面 抵抗は 2 X 1015Ω/口であった。 ポリカーボネート基 板の表面抵抗は 2. 7 X 1016ΩΖΕであり、 鉛筆硬度 は 2 Βである。
Figure imgf000027_0001
After immersing the magneto-optical disks obtained in Examples 1 to 21 and Comparative Example 1 in pure water at room temperature for 24 hours, the surface resistance was measured, but no change was observed. The surface resistance of Comparative Example 2 after the same treatment was 2 × 10 15 Ω / port. The surface resistance of the polycarbonate substrate is 2.7 × 10 16 ΩΖΕ and the pencil hardness is 2 2.
[実施例 22 ] [Example 22]
6官能ウレタンァクリレートオリゴマー （ U 1 226 Α, 新中村化学工業㈱製〉 40重量％， 6官能ァクリレ ートオリゴマー （ K A Y AR AD DPCA60 , 日本 化薬眯製） 20重量％, およびテトラエチレングリコ一 ルモノメタァクリレート （ブレンマー PE 200 , 日 本油脂㈱製〉 40重量％, 光開始剤 α—ヒドロキシイソ ブチルフエノン （ダロキュア 1 1 73 , メルク社製） 3 Phr からなる硬化性樹脂組成物を厚さ 1. 2mm、 直径 1 3〇 Mのポリカ一ボネ一ト基板のフラット面に約 1〇 mの厚さにスピンコート法により塗布し、 実施例 1〜2 1と同様に光硬化させた。 得られた基板の硬化面の表面 硬度は H Bであり、 表面抵抗は 2. 1 X 1013Ω.ΖΟで あった。 Hexafunctional urethane acrylate oligomer (U1226, manufactured by Shin-Nakamura Chemical Co., Ltd.) 40% by weight, Hexafunctional acrylate oligomer (KAY AR AD DPCA60, manufactured by Nippon Kayaku Co., Ltd.) 20% by weight, and tetraethylene glycol mono Methacrylate (Blemmer PE 200, manufactured by Nippon Oil & Fats Co., Ltd.) 40% by weight, photoinitiator α-hydroxyisobutylphenone (Darocur 1 173, manufactured by Merck) 3 Phr of curable resin composition of thickness 1 A flat surface of a polycarbonate substrate having a diameter of 2 mm and a diameter of 13 μM was applied to a thickness of about 1 μm by a spin coating method, and was photocured in the same manner as in Examples 1-21. The surface hardness of the cured surface of the substrate was HB, and the surface resistance was 2.1 × 10 13 Ω.ΖΟ.
[実施例 23 ] [Example 23]
ホスファゼンのへキサァクリレート （ U— 1 000， 出光石油化学㈱製〉 4 0重量％、 テトラァロピレンダリ コールモノメタァクリレート 〈ブレンマー P P— Hexaacrylate of phosphazene (U-1000, Made by Idemitsu Petrochemical Co., Ltd.> 40% by weight, tetraaropyrene glycol monomethacrylate <Blemmer PP—
33 0 , 日本油脂㈱製） 6 0重量％， 光開始剤ィルガキ ユア 90 7 (チバガイギ一社製〉 5 phr からなる硬化性 樹脂組成物を実施例 22と同様にポリカーボネー卜基板 に塗布し、 光硬化させた。 硬化塗膜の表面硬度は HBで表 面抵抗は 3. 6 X 1 0 ηΩ/Οであった。  A curable resin composition consisting of 330%, manufactured by Nippon Oil & Fat Co., Ltd., 60% by weight, and a photoinitiator, Irgaki Yua 907 (manufactured by Ciba Geigy Co., Ltd.), 5 phr, was applied to a polycarbonate substrate in the same manner as in Example 22, The cured coating film had a surface hardness of HB and a surface resistance of 3.6 X 10 ηΩ / Ο.
[実施例 24 ] [Example 24]
ホスファゼンのへキサァクリレート （ U— 1 0 00 , 出光石油化学㈱製） 3 0重量％、 テ.トラエチレングリコ ールモノメタァクリレート （ブレンマ一 ΡΕ— 20 0， 日本油脂㈱製） 70重量％， 光開始剤ィルガキュア  Hexaacrylate of phosphazene (U-100, manufactured by Idemitsu Petrochemical Co., Ltd.) 30% by weight, tetraethylene glycol monomethacrylate (Blemma 1-200, manufactured by NOF Corporation) 70% by weight, Photoinitiator Irgacure
907 〈チバガイギ一社製） 5 phr からなる硬化性樹脂 組成物を実施例 22と同様にポリ力一ボネ一ト基板に塗 布し、 光硬化させた。 硬化塗膜の表面硬度は HBで表面抵 抗は 5. 3 X 1 0 ^ΩΖΟであった。  907 (manufactured by Ciba Geigy Co., Ltd.) A curable resin composition consisting of 5 phr was applied to a polycarbonate substrate in the same manner as in Example 22 and light-cured. The surface hardness of the cured coating film was HB and the surface resistance was 5.3 X 10 ^ ΩΖΟ.
[実施例 2 5 ] [Example 25]
ホスファゼンのへキサァクリレート （ U— 1 0 0 〇， 出光石油化学眯製） 80重量％、 テトラエチレングリコ ールモノメタアタリレート （ブレンマー Ρ Ε— 2 0 0 , 日本油脂㈱製〉 2◦重量％, A I B N 5 phr からなる硬 化性樹脂組成物をポリカーボネート基板上に実施例 2 2 と同様に塗布し、 80でで熱硬化させた。 硬化塗膜の表 面硬度は Fで表面抵抗は 6. 3 X 1 014ΩΖΟであった, Hexaacrylate of phosphazene (U-100, manufactured by Idemitsu Petrochemical Co., Ltd.) 80% by weight, tetraethylene glycol monometaacrylate (Blenmer 200, manufactured by NOF Corporation) 2% by weight, AIBN A curable resin composition of 5 phr was coated on a polycarbonate substrate according to Example 22. And heat cured at 80. The surface hardness of the cured coating film was F and the surface resistance was 6.3 X 10 14 ΩΖΟ,
[実施例 26 ] [Example 26]
ホスファゼンのへキサァクリレート （ U— 1 000， 出光石油化学㈱製〉 80重量％、 メ トキシテトラエチレ ングリコールモノメタァクリレート 20重量％， A I B N 5 Phr からなる硬化性樹脂組成物を実施例 2 5と同様 にポリカーボネート基板上に塗布し、 熱硬化させた。 硬 化塗膜の表面硬度は Fで表面抵抗は 7. 3 X 1 014Ω/ □であった。 Phosphazene to the Kisaakurireto (U- 1 000, manufactured by Idemitsu Petrochemical Co., Ltd.> 80 wt%, main butoxy tetraethylate les glycol monomethacrylate § methacrylonitrile rate 20 wt%, implementing a curable resin composition comprising AIBN 5 P hr Example 2 The composition was applied on a polycarbonate substrate and thermally cured in the same manner as in 5. The cured film had a surface hardness of F and a surface resistance of 7.3 × 10 14 Ω / □.
[実施例 27 ] [Example 27]
6官能ウレタンァクリレートオリゴマー （ U 1 226 A 新中村化学工業㈱製） 4 ◦重量％, 6官能ァクリレート オリゴマー （ K A Y ARAD D P C A 6 0 , 日本化薬 ㈱製） 20重量％， およびテトラエチレングリコ一ルモ ノメタァクリレート （ライ トエステル DM, 共栄社油脂 ㈱製） 40重量％, 光開始剤ダロキュア 1 1 73 (メル ク社製〉 3phr からなる硬化性樹脂組成物を実施例 22 と同様にポリカーボネート基板に塗布し、 光硬化させた 得られたディスクの表面硬度は Fであり、 表面抵抗は 1 1 X 1 012ΩΖΕ1であった。 [実施例 28 ] Hexafunctional urethane acrylate oligomer (U1226A manufactured by Shin-Nakamura Chemical Co., Ltd.) 4% by weight, hexafunctional acrylate oligomer (KAY ARAD DPCA 60, manufactured by Nippon Kayaku Co., Ltd.) 20% by weight, and tetraethyleneglycol A curable resin composition consisting of 40% by weight of luminomethacrylate (Light Ester DM, manufactured by Kyoeisha Oil & Fats Co., Ltd.) and 3 phr of photoinitiator Darocure 1173 (manufactured by Merck) was applied to a polycarbonate substrate in the same manner as in Example 22. The coated and photocured disk had a surface hardness of F and a surface resistance of 11 × 10 12 ΩΖΕ1. [Example 28]
ホスファゼンのへキサァクリレート （ U— 1 000， 出 光石油化学㈱製〉 55重量％に燐酸モノエチレングリコ —ルメタァクリレート （ライ トエステル D M , 共栄社油 脂㈱製） 45重量％， 光開始剤ィルガキュア 9◦ 7 (チ バガイギ一社製） 5plir からなる硬化性樹脂組成物を実 施例 22と同様にポリカーボネート基板に塗布し、 光硬 化させた。 硬化塗膜の表面硬度は HBで表面抵抗は 3. 8X 1010ΩΖΕであった。 Hexaacrylate of phosphazene (U-1 000, manufactured by Idemitsu Petrochemical Co., Ltd.) 55% by weight of monoethylene glycol phosphate methacrylate (light ester DM, manufactured by Kyoeisha Oil Co., Ltd.) 45% by weight, photoinitiator Irgacure 9 ◦ 7 (manufactured by Ciba-Geigy Corporation) A curable resin composition consisting of 5 plir was applied to a polycarbonate substrate and light-cured in the same manner as in Example 22. The surface hardness of the cured coating was HB and the surface resistance was 3 8X 10 10 ΩΖΕ.
[実施例 2 ] [Example 2]
ホスファゼンのへキサァクリレート 〈 U— 1 000， 出 光石油化学㈱製） 95重量％に燐酸モノエチレングリコ ールメタァクリレート （ライ トエステル DM， 共栄社油 脂㈱製〉 5重量％， ラジカル開始剤 A I BN 5phr から なる硬化性樹脂組成物を実施例 25と同様にポリ力一ボ ネート基板上に塗布し、 熱硬化させた。 硬化塗膜の表面 硬度は H Bで表面抵抗は 5. 2 X 1 014ΩΖΙΙ]であった。 Hexaacrylate of phosphazene (U-1000, manufactured by Idemitsu Petrochemical Co., Ltd.) 95% by weight of monoethylene glycol methacrylate phosphate (light ester DM, manufactured by Kyoeisha Oil & Fat Co., Ltd.) 5% by weight, radical initiator AI BN A curable resin composition consisting of 5 phr was applied to a polycarbonate substrate and thermally cured in the same manner as in Example 25. The surface hardness of the cured coating film was HB and the surface resistance was 5.2 × 10 14. ΩΖΙΙ].
[実施例 30 ] [Example 30]
6官能ウレタンァクリレートオリゴマー （ U 1 226 Λ， 新中村化学工業㈱製） 40重量％, 6官能ァクリレ —トオリゴマー （ KAYARAD D P C A 60 , 日本 化薬眯製〉 40重量％， およびテトラエチレングリコー ルモノメタァクリレート （ホスマー M， 共栄社油脂糨製〉 20重量％, 光開始剤ダロキュア 1 1 73 (メルク社製〉 3 phr からなる硬化性樹脂組成物を実施例 22と同様に ポリカーボネート基板に塗布し、 光硬化させた。 得られ たディスクの表面硬度は HBであり、 表面抵抗は 1. 1 X 1 0 Ω,/Οであった。 Hexafunctional urethane acrylate oligomer (U1226, manufactured by Shin-Nakamura Chemical Co., Ltd.) 40% by weight, hexafunctional acrylate oligomer (KAYARAD DPCA 60, manufactured by Nippon Kayaku Co., Ltd.) 40% by weight, and tetraethylene glycol Lumonomethacrylate (Phosmer M, manufactured by Kyoeisha Yushi Co., Ltd.) 20% by weight, photoinitiator Darocure 1 173 (manufactured by Merck) A curable resin composition consisting of 3 phr was applied to a polycarbonate substrate in the same manner as in Example 22. The surface hardness of the obtained disk was HB, and the surface resistance was 1.1 × 10 Ω, / Ο.
「実施例 3 1 ] [Example 31]
ホスファゼンのへキサァクリレート （ U— 1 000， 出光石油化学㈱製） 99重量％にエチレングリコールモ ノメタァクリレートの燐酸モノエステルと トリェチルァ ミン 1 ： 1付加物 1重量％， 光開始剤ィルガキュア  Hexaacrylate of phosphazene (U-1000, manufactured by Idemitsu Petrochemical Co., Ltd.) 99% by weight of monoester of ethylene glycol monomethacrylate and triethylamine 1: 1 adduct 1% by weight, photoinitiator Irgacure
907 (チバガイギ一社製） 5phr からなる硬化性樹脂 組成物を実施例 22と同様にポリカーボネート基板に塗 布し、 光硬化させた。 硬化塗膜の表面硬度は 3Hで、 表面 抵抗は 8. 5 X 1 014ΩΖ口であった。 907 (manufactured by Ciba-Geigy Co., Ltd.) A curable resin composition consisting of 5 phr was applied to a polycarbonate substrate in the same manner as in Example 22 and light-cured. The surface hardness of the cured coating film was 3H, and the surface resistance was 8.5 × 10 14 Ω square.
[実施例 3 2 ] [Example 32]
ホスファゼンのへキサァクリレート （ U— 1 000， 出光石油化学㈱製） 99. 5重量％にエチレングリコ一 ルモノメタァクリレートの燐酸モノエステルと トリェチ ルアミン 1 ： 1付加物 0. 5重量％および A I B N 5 Phr からなる硬化性樹脂組成物を， 実施例 2 5と同様に ポリカーボネート基板上に塗布し、 熱硬化させた。 硬化 塗膜の表面硬度は 3Hで、 表面抵抗は 9. 5 X 1 014Ω □であった。 Hexaacrylate of phosphazene (U-1000, manufactured by Idemitsu Petrochemical Co., Ltd.) 99.5% by weight of phosphoric acid monoester of ethylene glycol monomethacrylate and triethylamine 1: 1 adduct 0.5% by weight and AIBN 5 A curable resin composition composed of Phr was applied on a polycarbonate substrate in the same manner as in Example 25, and was thermally cured. Hardening The surface hardness of the coating film was 3H, and the surface resistance was 9.5 × 10 14 Ω □.
[実施例 33 ] [Example 33]
CH2 =CH-C0(0CH2 CH2 ) A OH CH 2 = CH-C0 (0CH 2 CH 2 ) A OH
で表されるテトラエチレンダリコ一ルモノアクリレ一卜 3 〇重量％、 力プロラクトン変性ジペンタエリスリ トー ルへキサァクリレートとして D P CA 6 0を 2 0重量％ および D P C A 30を 2 0重量％、 ジペンタエリスリ ト —ルへキサァクリレート 20重量％、 へキサメチレング リコールジァクリレート 1 0重量％からなる組成物に、 光重合開始剤ィルガキュア 907 (チバガイギ一社製） を 3phr 含む硬化性樹脂組成物を調製した。 この組成物 の粘度は B型粘度計による 2 5。Cの測定で 1 . 3ボイズ であった。 この組成物を 8 mの厚さになるようにスピ ンコ一ト法により厚さ 1 . 2 mm、 直径 1 3 0 mmのポリ力 ーボネート基板のフラッ ト面に塗布した。 引き続き、 長 さ約 2 7 cm、 2 KWの高圧水銀灯を用い、 20 cmの高さ から紫外線を 1分簡照射し、 塗膜を硬化させた。  3% by weight of tetraethylene diol monoacrylate represented by the formula: 20% by weight of DPCA 60 and 20% by weight of DPCA 30 as dihexaerythritol hexyl acrylate. A curable resin composition containing 3 phr of a photopolymerization initiator Irgacure 907 (manufactured by Ciba-Geigy Corporation) in a composition comprising 20% by weight of oxamacrylate and 10% by weight of hexamethylene glycol diacrylate was prepared. The viscosity of this composition was 25 using a B-type viscometer. The value of C was 1.3 voise. This composition was applied to a flat surface of a polycarbonate substrate having a thickness of 1.2 mm and a diameter of 130 mm by a spin coating method so as to have a thickness of 8 m. Subsequently, using a high-pressure mercury lamp of about 27 cm in length and 2 KW, ultraviolet light was irradiated for 1 minute from a height of 20 cm to cure the coating film.
硬化後のポリ力一ボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
その結果、 表面鉛筆硬度は Hで、 表面抵抗は 1 . 〇 X 1 〇 13Ωノロであった。 また、 この硬化物塗膜をもつ基 板を 80 ， 85 %湿度の湿熟試験器中で耐候性試験を 2000時間行ったが、 試験の前後で硬化塗膜に変化は 認められなかった。 As a result, the surface pencil hardness is H, the surface resistivity was 1. 〇 X 1 〇 13 Omega Noro. The substrate with the cured coating film was subjected to a weather resistance test in a humidifier at 80 or 85% humidity. After 2000 hours, no change was observed in the cured coating before and after the test.
[実施例 34 ] [Example 34]
CH2 =CH-C0(0CH2 CH2 ) 6 OH CH 2 = CH-C0 (0CH 2 CH 2 ) 6 OH
で表されるへキサエチレンダリコールモノアクリレート 20重量％、 力アロラクトン変性ジペンタエリスリ ト一 ルへキサァクリレートとして D PCA 1 20を 30重量 %および D P C A 20を 20重量％、 ジペンタエリスリ トールへキサァクリレート 20重量％、 へキサメチレン グリコールジァクリレート 1 0重量％からなる組成物に、 光重合開始剤ィルガキュア 907 (チバガイギ一社製〉 を 5i>hr 含む硬化性樹脂組成物を調製した。 この組成物 の粘度は B型粘度計による 2 5 Cの測定で' 1. 1ボイズ であった。 この組成物を 1 O mの厚さになるように実 施例 3 3と同様にポリカーボネート基板に塗布し、 光硬 化させた。 20% by weight of hexaethylene dalicol monoacrylate represented by the following formula: 30% by weight of DPCA 120 and 20% by weight of DPCA 20 as dialloerythone-modified dipentaerythritol hexaacrylate, and 20% by weight of dipentaerythritol hexaacrylate. A curable resin composition containing 10% by weight of xamethylene glycol diacrylate and a photoinitiator Irgacure 907 (manufactured by Ciba Geigy Co., Ltd.) for 5i> hr was prepared, and the viscosity of the composition was B-type. As measured at 25 C with a viscometer, the result was' 1.1 vois. This composition was applied to a polycarbonate substrate in the same manner as in Example 33 so as to have a thickness of 1 Om, and was light-cured. Was.
硬化後のポリカーボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
硬化面の表面硬度は Hであり、 表面抵抗は 6. 5 X  The surface hardness of the hardened surface is H and the surface resistance is 6.5 X
1 013ΩΖΕ3であった。 1 0 13 ΩΖΕ3.
[実施例 3 5 ] [Example 35]
CH2 =CH-C0{0CH2 CH2 ) 5 OH で表されるペンタエチレンダリコールモノアクリレートCH 2 = CH-C0 (0CH 2 CH 2 ) 5 OH Pentaethylene dalicol monoacrylate represented by
30重量％、 力プロラクトン変性ジペンタエリスリ ト一 ルへキサァクリレートと して D PCA 60を 30重量％ および D P C A 30を 20重量％、 トリメチ口一ルァロ パントリアクリレート 1 0重量％、 へキサメチレングリ コ一ルジァクリレート 1 0重量％からなる組成物に、 光 重合開始剤ィルガキュア 907 (チバガイギ一社製〉 を 3p r 含む硬化性樹脂組成物を調製した。 この組成物の 粘度は B型粘度計による 25°Cの測定で 1. 8ボイズで あった。 この組成物を実施例 34と同様にポリ力一ボネ ート基板に塗布し、 光硬化させた。 30% by weight, 30% by weight of DPCA 60 and 20% by weight of DPCA 30 as di-proerythrone-modified dipentaerythrylhexaacrylate, 10% by weight of trimethyl-l-pan-triacrylate, 10% by weight of hexamethylene glycol A curable resin composition containing 3 p r of a photopolymerization initiator Irgacure 907 (manufactured by Ciba-Geigy Co., Ltd.) in a composition consisting of 10% by weight of lugia acrylate was prepared, and the viscosity of the composition was measured at 25 ° C using a B-type viscometer. This composition was applied to a polycarbonate substrate in the same manner as in Example 34, and was cured by light.
硬化後のポリ力一ボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
硬化面の表面硬度は Fであり、 表面抵抗は 1. I X 1 013ΩΖΕ1であった。 The surface hardness of the cured surface was F, and the surface resistance was 1. IX 10 13 ΩΖΕ1.
[実施例 36 ] [Example 36]
CH2 =CH-C0(0'CH2 CH2 ) 4 OH CH 2 = CH-C0 (0'CH 2 CH 2 ) 4 OH
で表されるテトラエチレンダリコールモノアクリレート 30重量％、 力アロラクトン変性ジペンタエリスリ ト一 ルへキサァクリレートと して D PCA 60を 35重量％ および DPCA 30を 35重量％からなる組成物に、 光 重合開始剤ィルガキュア 907 (チバガイギ一社製） を 3p r 舍む硬化性樹脂組成物を調製した。 この組成物の 粘度は B型粘度計による 25での測定で 2. 1ボイズで あった。 この組成物を実施例 34と同様にポリカーボネ ート基板に塗布し、 光硬化させた。 A photopolymerization initiator was added to a composition comprising 30% by weight of tetraethylene dalicol monoacrylate represented by the following formula, 35% by weight of DPCA 60 and 35% by weight of DPCA 30 as a hexaolactone-modified dipentaerythritol hexaacrylate. A curable resin composition containing 3g of Irgacure 907 (manufactured by Ciba Geigy) was prepared. Of this composition The viscosity was measured at 25 using a B-type viscometer and found to be 2.1 vois. This composition was applied to a polycarbonate substrate in the same manner as in Example 34, and photocured.
硬化後のポリカーボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
得られた硬化面の表面硬度は Fであり、 表面抵抗は 4. 3 X 1 013ΩΖΕ1であった。 The surface hardness of the obtained cured surface was F, and the surface resistance was 4.3 × 10 13 ΩΖΕ1.
[実施例 37 ] [Example 37]
CH2 =CH{CH3 }-C0(0CH2 CH2 ) 4 OH CH 2 = CH {CH 3 } -C0 (0CH 2 CH 2 ) 4 OH
で表されるテトラエチレンダリコールモノメタクリレ一 ト 30重量％、 力プロラクトン変性ジペンタエリスリ ト —ルへキサァクリレートとして D PCA 60を 3 5重量 %および D P CA 30を 3 5重量％からなる組成物に、 光重合開始剤ィルガキュア 907 (チバガイギ一社製〉 を 3 p 含む硬化性樹脂組成物を調製した。 この組成物 の粘度は B型粘度計による 25での測定で 1. 9ボイズ であった。 この組成物を実施例 34と同様にポリ力一ボ ネート基板に塗布し、 光硬化させた。 A composition consisting of 30% by weight of tetraethylene dalicol monomethacrylate represented by the formula, 35% by weight of DPCA 60 and 35% by weight of DPCA 30 as dihexaerythritol modified dipentaerythritol. A curable resin composition containing 3 p of a photopolymerization initiator Irgacure 907 (manufactured by Ciba-Geigy Co., Ltd.) was prepared, and the viscosity of the composition was 1.9 vise as measured with a B-type viscometer at 25. This composition was applied to a polycarbonate substrate as in Example 34 and photocured.
硬化後のポリカーボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
硬化面の表面硬度は Fであり、 表面抵抗は 5. 8 X The surface hardness of the hardened surface is F and the surface resistance is 5.8 X
1013ΩΖΕ1であった。 [実施例 38 ] 10 13 ΩΖΕ1. [Example 38]
CH2 =CH(CH3 )-C0(0CH2 CH2 ) 4 OH CH 2 = CH (CH 3 ) -C0 (0CH 2 CH 2 ) 4 OH
で表されるテトラエチレングリコールモノメタクリレー ト 3 0重量％、 力アロラクトン変性ジペンタエリスリ ト 一ルへキサァクリレ一トとして D P CA 1 20を 3 0重 量％および D P C A 20を 3 0重量％、 へキサメチレン グリコ一ルジァクリレート 1 0重量％からなる組成物に 光重合開始剤ダロキュア 1 1 73 (メルク社製〉 を 3 Phr 含む硬化性樹脂組成物を調製した。 この組成物の粘 度は B型粘度計による 2 5°Cの測定で 0. 98ボイズで あった。 この組成物を実施例 34と同様にポリ力一ボネ ート基板に塗布し、 光硬化させた。 ·  30% by weight of tetraethylene glycol monomethacrylate represented by the following formula: 30% by weight of DPCA 120 and 30% by weight of DPCA 20 as a hexa-allactone-modified dipentaerythritol hexaacrylate; hexamethylene glycol A curable resin composition containing 3 Phr of a photopolymerization initiator Darocure 1 173 (manufactured by Merck) in a composition consisting of 10% by weight of mono-diacrylate was prepared. It was 0.98 boise at a measurement of 5 ° C. This composition was applied to a polycarbonate substrate in the same manner as in Example 34 and photocured.
硬化後のポリカーボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
硬化面の表面硬度は Fであり、 表面抵抗は 4. I X 1 013ΩΖΕ1であった。 The surface hardness of the cured surface was F, and the surface resistance was 4. IX 10 13 ΩΖΕ1.
[実施例 39 ] [Example 39]
CH2 =CH-C0{0CH2 CH2 ) 6 OH CH 2 = CH-C0 {0CH 2 CH 2 ) 6 OH
で表されるへキサエチレンダリコ一ルモノアクリレ一ト 2〇重量％、 力アロラクトン変性ジペンタエリスリ トー ルへキサァクリレートと して D P CA 6 0を 3 0重量％ および D P C A 3 0を 2◦重量％、 トリメチ口一ルァロ パントリアク リレート 2 0 %、 テトラヒ ドロフルフリル ァクリレ一ト 1 0重量％からなる組成物に、 光重合開始 剤ィルガキュア 907 〈チバガイギ一社製） を 3phr 含 む硬化性樹脂組成物を調製した。 この組成物の粘度は B 型粘度計による 25 Cの測定で 1. 1ボイズであった。 この組成物を実施例 34と同様にポリカーボネート基板 に塗布し、 光硬化させた。 2% by weight of hexene ethylene diol monoacrylate represented by the following formula: 30% by weight of DPCA 60 and 2% by weight of DPCA 30 as a hexaolacrylate modified dipentaerythritol hexaacrylate; 20% per liter pantoliac acrylate, tetrahydrofurfurfuryl A curable resin composition containing 3 phr of a photopolymerization initiator Irgacure 907 (manufactured by Ciba-Geigy Corporation) in a composition consisting of 10% by weight of acrylate was prepared. The viscosity of this composition was 1.1 Boys as measured at 25 C by a B-type viscometer. This composition was applied to a polycarbonate substrate in the same manner as in Example 34, and photocured.
硬化後のポリカーボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
硬化面の表面硬度は Hであり、 表面抵抗は 6. 5 X 1 0 " ロであった。  The surface hardness of the cured surface was H, and the surface resistance was 6.5 × 10 ″ b.
[実施例 40 ] [Example 40]
CH2 =CH-C0(0CH2 CH2 ) 6 OH CH 2 = CH-C0 (0CH 2 CH 2 ) 6 OH
で表されるへキサエチレングリコ一ルモノアクリレート 2 5重量％、 力アロラクトン変性ジペンタエリスリ トー ルへキサァクリレートとして D PCA 60を 30重量％ および D P C A 20を 3 5重量％、 ネオペンチルグリコ —ルジァクリレート 1 ◦重量％からなる組成物に、 光重 合開始剤ィルガキュア 9 07 (チバガイギ一社製〉 を 4 Phr 含む硬化性樹脂組成物を調製した。 この組成物の粘 度は B型粘度計による 2 5°Cの測定で 2. 3ポィズであ つた。 この組成物を実施例 34と同様にポリカーボネ一 ト基板に塗布し、 光硬化させた。 25% by weight of hexaethylene glycol monoacrylate represented by the following formula: 30% by weight of DPCA 60 and 35% by weight of DPCA 20 as a dialloerythone-modified dipentaerythritol hexaacrylate, neopentylglycol-l-diacrylate 1 ◦% by weight A curable resin composition containing 4 Phr of a photopolymerization initiator Irgacure 907 (manufactured by Ciba-Geigy Co., Ltd.) was prepared for the composition consisting of: The viscosity of this composition was measured at 25 ° C using a B-type viscometer. The composition was 2.3 poises .. The composition was applied to a polycarbonate substrate and light-cured in the same manner as in Example 34.
硬化後のポリカーボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。 For the cured surface of the polycarbonate substrate after curing, see Table The sheet resistance and pencil hardness were measured.
硬化面の表面硬度は Fであり、 表面抵抗は 6. 9 X 1 013ΩΖΟであった。 The surface hardness of the cured surface was F, and the surface resistance was 6.9 × 10 13 ΩΖΟ.
[実施例 4 1 ] [Example 4 1]
CH2 =C (CH3 }-C0(0CH2 CH 2 ) 4 OH CH 2 = C (CH 3 } -C0 (0CH 2 CH 2) 4 OH
で表されるテトラエチレンダリコ一ルモノメタクリレー ト 3 0重量％、 力アロラクトン変性ジペンタエリスリ ト —ルへキサァクリレートとして D P CA 1 20を 5 0重 量％、 ヒドロキシピバリン酸ネオペンチルダリコールジ ァクリレート 1 0重量％、 グリセ口一ルジメタァクリレ —ト 1 0重量％からなる組成物に、 光重合開始剤ィルガ キュア 90 7 (チバガイギ一社製〉 を 5 phr 含む硬化性 樹脂組成物を調製した。 この組成物の粘度は B型粘度計 による 2 5。Cの測定で 2. 6ボイズであった。 この組成 物を実施例 34と同様にポリカーボネート基板に塗布し、 光硬化させた。  30% by weight of tetraethylene dimethyl monomethacrylate represented by the following formula: 50% by weight of DPCA120 as a dialloerythone-modified dipentaerythritol-hexahexyl acrylate, and 10% by weight of neopentyldaricol diacrylate hydroxypivalate A curable resin composition containing 5 phr of a photopolymerization initiator Irgacure 907 (manufactured by Ciba-Geigy Corporation) in a composition consisting of 10% by weight of glycerol and 10% by weight of glycerol / dimethacrylate was prepared. The viscosity was measured by a B-type viscometer at 25. The measured viscosity at C was 2.6 V. This composition was applied to a polycarbonate substrate in the same manner as in Example 34, and photocured.
硬化後のポリ力一ボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
硬化面の表面硬度は Fであり、 表面抵抗は 9. 8 X  The surface hardness of the hardened surface is F and the surface resistance is 9.8 X
1 〇 13ΩΖΕ]であった。 ' 1 〇 13 ΩΖΕ]. '
[実施例 42 ] [Example 42]
CH2 =CH-C0(.0CH2 CH2 ) 4 OH で表されるテトラエチレングリコールモノアクリレ一トCH 2 = CH-C0 (.0CH 2 CH 2 ) 4 OH Tetraethylene glycol monoacrylate represented by
30重量％、 力アロラクトン変性ジペンタエリスリ ト一 ルへキサァクリレートとして D PCA 60を 60重量％、 及びペンタエリスリ トールテトラァクリレート 1 0重量 %からなる組成物に、 光重合開始剤ィルガキュア 907 (チバガイギ一社製） を 3pl 含む硬化性樹脂組成物を 調製した。 この組成物の粘度は B型粘度計による 2 の測定で 3. 3ボイズであった。 この組成物を実施例 3 4と同様にポリカーボネート基板に塗布し、 光硬化させ た。 A composition comprising 30% by weight, 60% by weight of DPCA 60 as a dialloerythrone-modified dipentaerythryl hexacrylate, and 10% by weight of pentaerythritol tetraacrylate is added to a photopolymerization initiator Irgacure 907 (manufactured by Ciba Geigy Corporation) A curable resin composition containing 3 pl of was prepared. The viscosity of this composition was 3.3 Boyes as measured by a B-type viscometer in 2 steps. This composition was applied to a polycarbonate substrate in the same manner as in Example 34 and photocured.
硬化後のポリカーボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
硬化面の表面硬度は Hであり、 表面抵抗は 2. 8 X 1 013ΩΖΕ1であった。 The surface hardness of the cured surface was H, and the surface resistance was 2.8 × 10 13 ΩΖΕ1.
[実施例 43 ] [Example 43]
CH2 =CH-C0[0CH2 CH (CH3 }]4 OH CH 2 = CH-C0 [0CH 2 CH (CH 3 }) 4 OH
で表されるテトラプロピレングリコールモノアクリレー ト 30重量％、 力アロラクトン変性ジペンタエリスリ ト 一ルへキサァクリレートとして D P CA 6 0を 60重量 30% by weight of tetrapropylene glycol monoacrylate represented by the following formula: 60% by weight of DPCA 60 as a hexaacrylate of dipentaerythritol modified with force allolactone
%、 及びペンタエリスリ トールテトラァクリレ一ト 1 0 重量％からなる組成物に、 光重合開始剤ィルガキュア 907 (チバガイギ一社製） を 3piir 含む硬化性樹脂組 成物を調製した。 この組成物の粘度は B型粘度計による 2 5°Cの測定で: 3. 3ボイズであった。 この組成物を実 施例 34と同様にポリカーボネート基板に塗布し、 光硬 化させた。 %, And 10% by weight of pentaerythritol tetraacrylate to prepare a curable resin composition containing 3 piir of a photopolymerization initiator Irgacure 907 (manufactured by Ciba-Geigy Corporation). The viscosity of this composition is measured using a B-type viscometer. Measured at 25 ° C .: 3.3. This composition was applied to a polycarbonate substrate in the same manner as in Example 34, and photocured.
硬化後のポリカーボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
硬化面の表面硬度は Fであり、 表面抵抗は 5. 8 X The surface hardness of the hardened surface is F and the surface resistance is 5.8 X
1 013Ω/[]であった。 [比較例 3 ] 10 13 Ω / []. [Comparative Example 3]
力プロラク卜ン変性ジペンタエリスリ 卜一ルへキサァク リレートの D P CA 6 0を 3 0重量％および D P C A 3 0を 30重量％、 ジペンタエリスリ トールへキサァクリ レ一ト 20重量％、 へキサメチレングリコ一ルジァクリ レ一ト 20重量％からなる組成物に、 光重合開始剤ィル ガキュア 9◦ 7 (チバガイギ一社製〉 を 3 phr 含む硬化 性樹脂組成物を調製した。 この組成物の粘度は B型粘度 計による 2 5。Cの測定で 3. 3ボイズであった。 この組 成物を実施例 3 3と同様に厚さ 1 · 2 mm、 直径 1 3 0 mm のポリカーボネ一ト基板のフラッ 卜面に 8 mの厚さに なるようにスピンコート法により塗布し、 引き続き、 長 さ約 27 cm、 2 KWの高圧水銀灯を用い、 2 0 cmの高さ から紫外線を 1分藺照射し、 塗膜を光硬化させた。 30% by weight of DPCA 60 and 30% by weight of DPCA 30 in dipentaerythritol hexaacrylate modified with dipentaerythritol, 20% by weight of dipentaerythritol hexaacrylate, 20% by weight of hexamethylene glycol diacrylate A curable resin composition containing 3 phr of a photopolymerization initiator il Gacure 9◦7 (manufactured by Ciba Geigy Co., Ltd.) in a composition consisting of 20% by weight was prepared using a B-type viscometer. 25. The measured value of C was 3.3 V. This composition was placed on the flat surface of a polycarbonate substrate having a thickness of 1.2 mm and a diameter of 130 mm in the same manner as in Example 33. m to a thickness of 20 m, and then apply UV light from a height of 20 cm for 1 minute using a high-pressure mercury lamp of about 27 cm in length and 2 KW to illuminate the coating film. Cured.
硬化後のポリカーボネートディスクの硬化面について、 表面抵抗および鉛筆硬度を測定した。 その結果表面鉛筆硬度は Hで、 表面抵抗は 6. 5 X 1 015ΩΖΕ3であった。 The surface resistance and pencil hardness of the cured surface of the cured polycarbonate disk were measured. As a result, the surface pencil hardness was H, and the surface resistance was 6.5 × 10 15 ΩΖΕ3.
[実施例 44 ] [Example 44]
厚さ 1. 2践、 直径 130mmのポリ力一ボネート基板 のフラット面に硬化性樹脂組成物 （ N SC— 7106、 日本精化麴製） 96重量％、 下記化合物 （ M A 1 50、 日本乳化剤㈱製） 4重量％の組成物に、 ドデシルペンゼ ンスルホン酸ナトリウム 0. 1 phr を含むとの混合物を 実施例 34と同様に 10 mの厚さになるようにスピン コート法により塗布し、 引き続き、 長さ約 27cm、 2 K wの高圧水銀灯を用い、 20 cmの高さから紫外線を 1分 間照射し、 塗膜を光硬化させた。  Curing resin composition (NSC-7106, manufactured by Nippon Seika) 96% by weight on the flat surface of a polycarbonate substrate with a diameter of 130mm and a diameter of 130mm, the following compound (MA150, Nippon Emulsifier) A mixture of 4% by weight of a composition containing 0.1 phr of sodium dodecyl benzene sulfonate was applied by spin coating to a thickness of 10 m in the same manner as in Example 34. Ultraviolet rays were irradiated for 1 minute from a height of 20 cm using a high-pressure mercury lamp of about 27 cm and 2 Kw, and the coating was photocured.
CH3 CH 3
CH2 = C-C0(0CH2 CH2 ) i50H 硬化後のポリカーボネート基板の硬化面について、 表面 抵抗および鉛筆硬度を測定した。 鉛筆硬度は Ηであり、 表面抵抗は 9. 8 X 1013ΩΖ口であった。 About CH 2 = C-C0 (0CH 2 CH 2) i 5 0H cured surface of the polycarbonate substrate after curing, it was measured surface resistance and pencil hardness. The pencil hardness was Η and the surface resistance was 9.8 × 10 13 ΩΖ.
[比較例 4 ] [Comparative Example 4]
厚さ 1. 2mm、 直径 1 3 Omniのポリカーボネート基板 のフラット面に硬化性樹脂組成物 （N SC— 7106、 闩本精化㈱製） を 96重量％、 実施例 44に記載の化合 物 （ MA 1 50、 日本乳化剤㈱製〉 を 4重量％含む混合 物を実施例 44と同様に 1 0 mの厚さになるようにス ピンコート法により塗布し、 引き続き、 長さ約 27 cm、 2 Kwの高圧水銀灯を用い、 20 cmの高さから紫外線をOn a flat surface of a polycarbonate substrate having a thickness of 1.2 mm and a diameter of 13 Omni, a curable resin composition (NSC-7106, manufactured by Nippon Seika) was 96% by weight, and the compound described in Example 44 (MA 1 50, 4% by weight of Japan Emulsifier Co., Ltd. The product was applied by spin coating to a thickness of 10 m in the same manner as in Example 44, and then UV rays were applied from a height of 20 cm using a high-pressure mercury lamp of about 27 cm in length and 2 Kw.
1分間照射し、 塗膜を光硬化させた。 硬化後のポリ力一 ボネート基板の硬化面について、 表面抵抗および鉛筆硬 度を測定した。 鉛筆硬度は Hであったが、 表面抵抗は 1. 2 X 1 015ΩΖ{Ι1であった。 The coating was light cured for 1 minute. The surface resistance and pencil hardness of the cured surface of the cured polycarbonate substrate were measured. The pencil hardness was H, but the surface resistance was 1.2 × 10 15 ΩΖ {Ι1.
[実施例 45 ] [Example 45]
6官能ウレタンァクリレートオリゴマー （ U 1 226 Α, 新中村化学工業㈱製） 50重量％、 トリメチロール ァロパントリアクリレート 40重量％、 およびテトラエ チレンダリコールモノメタァクリレート 1 0重量％の組 成物に、 トデシルベンゼンスルホン酸ナトリウム 1 phr 、 光開始剤ダロキュア 1 1 73 (メルク社製〉 3 phr を含 む硬化性樹脂組成物を実施例 34と同様にポリカーボネ ート基板に塗布し、 光硬化させた。 基板の硬化面の表面 硬度は Fであり、 表面抵抗は 3. 6 Χ 1 013ΩΖΟであ つた。 Hexafunctional urethane acrylate oligomer (U1226Α, manufactured by Shin-Nakamura Chemical Co., Ltd.) 50% by weight, trimethylol aropan triacrylate 40% by weight, and tetraethylene glycol monomethacrylate 10% by weight A curable resin composition containing 1 phr of sodium todecylbenzenesulfonate and 3 phr of a photoinitiator Darocure 1173 (manufactured by Merck) was applied to the polycarbonate substrate in the same manner as in Example 34. The cured surface of the substrate had a surface hardness of F and a surface resistance of 3.6Χ10 13 ΩΖΟ.
[比較例 5 ] [Comparative Example 5]
6官能ウレタンァクリレートオリゴマー （ U 1 226 Α, 新中村化学工業㈱製） 50重量％、 トリメチロール ァロパントリァクリレート 40重量％、 およびテトラエ チレンダリコールモノメタァクリレート 1 ◦重量％、 光 開始剤ダロキュア 1 1 73 (メルク社製） を 3phr 舍む 硬化性樹脂組成物を実施例 4 5と同様にポリ力一ボネ一 ト基板に塗布し、 光硬化させた。 基板の硬化面の表面硬 度は Fであり、 表面抵抗は 1. 0 5 Χ 1 015ΩΖΕ1であ つた。 Hexafunctional urethane acrylate oligomer (U1226Α, manufactured by Shin-Nakamura Chemical Co., Ltd.) 50% by weight, trimethylol aropantriacrylate 40% by weight, and tetrae 1 phr weight of Tylendalcol monomethacrylate, 3 phr of Darocur 1 173 (manufactured by Merck) photoinitiator The curable resin composition was applied to a polycarbonate substrate in the same manner as in Example 45. Coated and light cured. Surface hardness of the cured surface of the substrate is F, surface resistance 1. 0 5 Χ 1 0 15 ΩΖΕ1 der ivy.
[実施例 46 ] [Example 46]
ホスファゼンのへキサァクリレー卜 （ U— 1 000 , 出光石油化学㈱製〉 70重量％、 テトラプロピレンダリ コールモノメタァクリレート 30重量％、 アバネル Hexaacrylate of phosphazene (U-1 000, manufactured by Idemitsu Petrochemical Co., Ltd.) 70% by weight, tetrapropylene d'alicole monomethacrylate 30% by weight, Avanel
S 74 (アルキルエーテルスルホン酸ナトリウム ； 日本 油脂㈱製） 0. Γ P h K 、 光開始剤ィルガキュア 907 (チバガイギ一社製） 3phr からなる硬化性樹脂組成物 を実施例 34と同様にポリ力一ボネ一卜基板に塗布し、 光硬化させた。 硬化塗膜の表面硬度は Hで表面抵抗は 3. 5 X 1 012ΩΖ口であった。 S 74 (sodium alkyl ether sulfonate; manufactured by Nippon Yushi Co., Ltd.) 0. The curable resin composition comprising PhK and 3 phr of photoinitiator Irgacure 907 (manufactured by Ciba-Geigy Co., Ltd.) was prepared in the same manner as in Example 34. It was applied to a bottle substrate and light cured. The surface hardness of the cured coating film was H and the surface resistance was 3.5 × 10 12 ΩΖ.
[実施例 47 ] [Example 47]
力アロラクトン変性ジペンタエリスリ トールへキサァ クリレート （ D P CA 60 ； 日本化薬㈱製〉 6 ◦重量％ トリメチロールァロパントリアクリレ一ト 20重量％、 テトラエチレングリコールモノアクリレート 20重量％ の組成物に、 ダイヤポン L (ラウロイルメチルタウリン 酸ナトリウム ； 日本油脂鰓製〉 2phr 、 光開始剤ィルガ キュア 9 07 (チバガイギ一社製〉 3 phr を含む硬化性 樹脂組成物を実施例 34と同様にポリカーボネート基板 に塗布し、 光硬化させた。 硬化塗膜の表面硬度は Fで表 面抵抗は 6. 2 X 1 0130ノロであった。 Strength allolactone-modified dipentaerythritol hexaacrylate (DPCA 60; manufactured by Nippon Kayaku Co., Ltd.) 6% by weight Trimethylol aropantriacrylate 20% by weight, tetraethylene glycol monoacrylate 20% by weight L (Lauroylmethyltaurine A curable resin composition containing 2 phr sodium nitrate; manufactured by Nippon Oil Gill Co., Ltd .; 2 phr, and 3 phr of a photoinitiator, IRGA CURE 907 (manufactured by Ciba Geigy) was applied to a polycarbonate substrate in the same manner as in Example 34, followed by photocuring. The surface hardness of the cured coating film was F and the surface resistance was 6.2 × 10 130 .
[実施例 48 ] [Example 48]
CH2 =CH-C0{0CH2 CH2 ) 4 OH CH 2 = CH-C0 {0CH 2 CH 2 ) 4 OH
で表されるテトラエチレンダリコールモノアクリレート Tetraethylene dalicol monoacrylate represented by
1 0重量％、 力アロラクトン変性ジペンタエリスリ トー ルへキサァクリレートとして D P CA 60を 30重量％ および D P C A 30を 30重量％、 ジペンタエリスリ ト —ルへキサァクリレ一ト 20重量％、 へキサメチレング リコールジァクリレ一ト 1 0重量％からなる組成物に、 ドデシルベンゼンスルホン酸ナトリウム 0. 5phr 、 光 重合開始剤ィルガキュア 907 (チバガイギ一社製〉 を 3p r 含む硬化性樹脂組成物を調製した。 この組成物の 粘度は B型粘度 †をによる 25での測定で 1 . 9ボイズ であった。 この組成物を実施例 34と同様に 1 0 jumの 厚さになるようにスピンコ一ト法により厚さ 1 . 2mm、 直径 1 3 O Mのポリカーボネート基板のフラット面に塗 布し、 引き続き、 長さ約 27 cm、 2 KWの高圧水銀灯を 用い、 2 O cmの高さから紫外線を 1分間照射し、 塗膜を 硬化させた。 硬化後のポリカーボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。 10% by weight, 30% by weight of DPCA 60 and 30% by weight of DPCA 30 as dialloerythone-modified dipentaerythritol hexacrylate, 20% by weight of dipentaerythritol-l-hexaacrylate, 20% by weight of hexamethylene glycol diacrylate A curable resin composition containing 0.5% by weight of sodium dodecylbenzenesulfonate and 3pr of a photopolymerization initiator Irgacure 907 (manufactured by Ciba-Geigy Corporation) was prepared in a composition consisting of 10% by weight. The B-type viscosity was measured to be 1.9 vois by measurement at 25. The composition was spin-coated to a thickness of 10 mm, as in Example 34, to a thickness of 10 jum. Apply it to the flat surface of a polycarbonate substrate with a diameter of 13 OM, and then irradiate ultraviolet rays for 1 minute from a height of 2 Ocm using a high-pressure mercury lamp of about 27 cm in length and 2 KW to harden the coating. It was. The surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
その結果、 表面鉛筆硬度は Hで、 表面抵抗は 2. 6 X 1 〇 13ΩΖΕ1であった。 また、 この硬化物塗膜をもつ基 板を 8 CTC, 85%湿度の湿熱試験器中で耐候性試験を 2000時間行ったが、 試験の前後で硬化塗膜に変化は 認められなかった。 As a result, the surface pencil hardness at H, the surface resistance 2. were 6 X 1 〇 13 ΩΖΕ1. The substrate having the cured product coating film was subjected to a weather resistance test for 2000 hours in a wet heat tester at 8 CTC and 85% humidity, but no change was observed in the cured coating film before and after the test.
[比較例 6 ] [Comparative Example 6]
CH2 =CH-C0(0CH2 CH2 ) 4 OH CH 2 = CH-C0 (0CH 2 CH 2 ) 4 OH
で表されるテトラエチレンダリコールモノアクリレート 1 0重量％、 力アロラクトン変性ジペンタエリスリ ト一 ルへキサァクリレートとして DPCA60を 30重量％ および D P C A 30を 30重量％、 ジペンタエリスリ ト —ルへキサァクリレート 20重量％、 へキサメチレング リコールジァクリレート 1 0重量％からなる組成物、 光 重合開始剤ィルガキュア 907 (チバガイギ一社製） を 3P r 含む硬化性樹脂組成物を調製した。 10% by weight of tetraethylene dalicol monoacrylate represented by the following formula: 30% by weight of DPCA60 and 30% by weight of DPCA30 as a dialloerythone-modified dipentaerythrylhexaacrylate, 20% by weight of dipentaerythryl-hexaacrylate, 20% by weight of hexamethylene glycol recall di § chestnut rate 1 0 wt% composition comprising and a photopolymerization initiator Irugakyua 907 (Ciba-Geigy Ltd. one company) and 3-curable resin composition comprising P r was prepared.
この組成物を実施例 48と同様にポリ力一ボネート基 板に塗布し、 光硬化させた。  This composition was applied to a polycarbonate substrate as in Example 48 and photocured.
硬化後のポリ力一ボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
その結果、 表面鉛筆硬度は Hで、 表面抵抗は 1. 1 X 1 015ΩΖΕであった。 [実施例 49 ] As a result, the surface pencil hardness was H and the surface resistance was 1.1 × 10 15 ΩΖΕ. [Example 49]
CH2 =CH-C0{0CH2 CH2 ) 6 OH CH 2 = CH-C0 {0CH 2 CH 2 ) 6 OH
で表されるへキサエチレンダリコールモ.ノアクリレート Hexaethylenedalicolmo.noacrylate represented by
1 〇重量％、 力アロラクトン変性ジペンタエリスリ ト一 ルへキサァクリレ一トと して D P CA 1 20を 3 0重量 %および D PC A 20を 3 0重量％、 ジペンタエリスリ ト一ルへキサァクリレート 20重量％、 へキサメチレン ダリコ一ルジァクリレ一ト 1 0重量％からなる組成物に, ドデシルベンゼンスルホン酸ナトリウム l phr 、 光重合 開始剤ィルガキュア 90 7 (チバガイギ一社製） を 5 Phr 含む硬化性樹脂組成物を調製した。 この組成物の粘 度は B型粘度計をによる 2 5での測定で 1. 7ボイズで あった。 この組成物を実施例 34と同様に 1 0 >amの厚 さになるようにスピンコート法によりポリカーボネート 基板のフラッ ト面に塗布し、 引き続き、 長さ約 27 cm、 2 KWの高圧水銀灯を用い、 20 cmの高さから紫外線を 1分間照射し、 塗膜を光硬化させた。 硬化後のポリ力 ーボネート基板の硬化面について、 表面抵抗および鉛筆 硬度を測定した。 1% by weight, 30% by weight of DPCA 120 and 30% by weight of DPCA 20 as diacrylates modified dipentaerythryl hexaacrylate, 20% by weight of dipentaerythryl hexaacrylate A curable resin composition was prepared which contained 10% by weight of xamethylene dimethyl alcohol, 1 phr of sodium dodecylbenzenesulfonate and 5 Phr of a photopolymerization initiator irgacure 907 (manufactured by Ciba-Geigy Corporation). The viscosity of this composition was 1.7 voise as measured by a B-type viscometer at 25. This composition was applied to the flat surface of a polycarbonate substrate by spin coating so as to have a thickness of 10> am in the same manner as in Example 34, and then a high-pressure mercury lamp of about 27 cm in length and 2 KW was used. Ultraviolet rays were irradiated from a height of 20 cm for 1 minute to photo-cur the coating film. The surface resistance and pencil hardness of the cured surface of the polycarbonate substrate after curing were measured.
硬化面の表面硬度は Hであり、 表面抵抗は 1. 5 X 1 013Ω/0であった。 The surface hardness of the cured surface was H, and the surface resistance was 1.5 × 10 13 Ω / 0.
[比較例 7 ] [Comparative Example 7]
CH2 =CH-C0{0CH2 CH2 ) e OH で表されるへキサエチレングリコ一ルモノアクリレートCH 2 = CH-C0 {0CH 2 CH 2 ) e OH Hexaethylene glycol monoacrylate represented by
1 0重量％、 力アロラクトン変性ジペンタエリスリ ト一 ルへキサァクリレートと して D P CA 1 2 0を 3 0重量 %および D P C A 2 0を 3 0重量％、 ジペンタエリスリ トールへキサァクリレート 2 0重量％、 へキサメチレン グリコールジァクリレート 1 0重量％からなる組成物に、 光重合開始剤ィルガキュア 9 0 7 (チバガイギ一社製〉 を 5 phr 含む硬化性樹脂組成物を調製した。 この組成物 の粘度は B型粘度計をによる 2 5°Cの測定で 1 . 7ボイ ズであった。 この組成物を実施例 4 9と同様にポリ力 一ボネ一ト基板に塗布し、 光硬化させた。 10% by weight, 30% by weight of DPCA120 and 30% by weight of DPCA20 as dialloerythone-modified dipentaerythritol hexaacrylate, 20% by weight of dipentaerythritol hexaacrylate, 20% by weight of hexamethylene glycol diacrylate A curable resin composition containing 5 phr of a photopolymerization initiator Irgacure 907 (manufactured by Ciba Geigy Corporation) in a composition comprising 10% by weight of acrylate was prepared. The composition was 1.7 voices as measured at 25 ° C. This composition was applied to a polycarbonate substrate in the same manner as in Example 49 and photocured.
硬化後のポリカーボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
硬化面の表面硬度は Hであり、 表面抵抗は 1 . 5 X 1015ΩΖΕ3であった。 The surface hardness of the cured surface was H, and the surface resistance was 1.5 × 10 15 ΩΖΕ3.
[実施例 5 0 ] [Example 50]
CH2 =CH-C0(0CH2 CH2 ) s OH CH 2 = CH-C0 (0CH 2 CH 2 ) s OH
で表されるペンタエチレングリコ一ルモノアクリレート 5重量％、 力プロラクトン変性ジペンタエリスリ トール へキサァクリレートとして D P CA 6 0を 4 5重量％ぉ よび D P C A 3 0を 20重量％、 トリメチロールァロパ ントリァクリレート 2 0重量％、 へキサメチレンダリコ —ルジァクリレート 1 0重量％からなる組成物に、 アル キルエーテルスルホン酸ナトリウム （アバネル S 70 ； 日本油脂㈱製） l phr 、 光重合開始剤ィルガキュア 5% by weight of pentaethyleneglycol monoacrylate represented by the following formula: 45% by weight of DPCA 60 as a di-proerythritol-modified hexacrylate, and 20% by weight of DPCA 30 as trihexyrolitol triacrylate A composition comprising 20% by weight of hexamethylene darico-diacrylate and 10% by weight of Sodium kill ether sulfonate (Avanel S70; manufactured by NOF Corporation) l phr, photopolymerization initiator irgacure
907 (チバガイギ一社製〉 を 3piir 含む硬化性樹脂組 成物を調製した。 この組成物の粘度は B型粘度計をによ る 25 Cの測定で 2. 1ボイズであった。 この組成物を 実施例 34と同様に 1 0 mの厚さになるようにスピン コート法によりポリカーボネート基板のフラッ ト面に塗 布し、 引き続き、 長さ約 27 cm、 2 KWの高圧水銀灯を 用い、 20 cmの高さから紫外線を 1分間照射し、 塗膜を 光硬化させた。  A curable resin composition containing 3 piir of 907 (manufactured by Ciba-Geigy Co., Ltd.) was prepared, and the viscosity of the composition was 2.1 Boys as measured at 25 C using a B-type viscometer. Was applied to the flat surface of the polycarbonate substrate by spin coating so as to have a thickness of 10 m in the same manner as in Example 34, and then a 20-cm high-pressure mercury lamp of about 27 cm in length and 2 KW was used. UV light was irradiated for 1 minute from the height of the film, and the coating film was photocured.
硬化後のポリ力一ボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
硬化面の表面硬度は Hであり、 表面抵抗は 3. I X 1 013ΩΖΕ]であった。 The surface hardness of the cured surface was H, and the surface resistance was 3. IX 10 13 ΩΖΕ].
[実施例 51 ] [Example 51]
CH2 =CH(CH3 )-C0(0CH2 CH2 ) 4 OH CH 2 = CH (CH 3 ) -C0 (0CH 2 CH 2 ) 4 OH
で表されるテトラエチレングリコールモノメタクリレー ト 20重量％、 力アロラクトン変性ジペンタエリスリ ト —ルへキサァクリレートと して DPCA 60を 45重量 %および DPCA 30を 35重量％からなる組成物に、 R { OCH2 CH2 0 ) n S03 N a {レべノール WX ； 花王㈱製） 1 Phr 、 光重合開始剤ィルガキユア 9〇 7A composition consisting of 20% by weight of tetraethylene glycol monomethacrylate represented by the following formula, and 45% by weight of DPCA 60 and 35% by weight of DPCA 30 as a di-alloacrylate modified dipentaerythritol-hexaacrylate, was added with R {OCH 2 CH 2 0) n S0 3 n a { leveling Nord WX; Kao Co., Ltd.) 1 Phr, photoinitiator Irugakiyua 9_Rei 7
(チバガイギ一社製〉 を 3phr 含む硬化性樹脂組成物を 調製した。 この組成物の粘度は B型粘度計をによる 2 5 。Cの測定で 2 . 0ボイズであった。 この組成物を実施例 5 0と同様にポリカーボネート基板に塗布し、 光硬化さ せた。 (Manufactured by Ciba Geigy Co., Ltd.) Prepared. The viscosity of this composition was 25 using a B-type viscometer. The measurement of C was 2.0 vois. This composition was applied to a polycarbonate substrate in the same manner as in Example 50, and photocured.
硬化後のポリカーボネート基板の硬化面について、 表 面抵抗および鉛筆硬度を測定した。  The surface resistance and the pencil hardness of the cured surface of the cured polycarbonate substrate were measured.
硬化面の表面硬度は Fであり、 表面抵抗は 6 . 8 X 1 〇 1 3 Ω Ζί3であった。 産業上の利用可能性 Surface hardness of the cured surface is F, the surface resistance was 6. 8 X 1 〇 1 3 Ω Ζί3. Industrial applicability
以上のように、 本発明は周知のコンパクトディスク ( C D〉 、 実用化がはじまった光磁気ディスク等の光デ イスクのハードコート層として、 耐久性に優れた帯電防 止性能と必要な表面硬度を有し、 また無溶媒でも形成可 能なハードコート層を実現するものであり、 高度な信頼 性が要求され、 特にホコリ， チリなどの異物の付着防止 が必須と言われる計算機の補助記憶装置用の光磁気ディ スク等の光デイスクに好適なものである。  As described above, the present invention provides a hard coat layer for an optical disk such as a well-known compact disk (CD) and a magneto-optical disk that has been put into practical use, and has an antistatic performance with excellent durability and a required surface hardness. It has a hard coat layer that can be formed even without solvent. It is required to have a high degree of reliability, especially for the auxiliary storage device of computers where it is essential to prevent the adhesion of foreign substances such as dust and dust. It is suitable for an optical disk such as a magneto-optical disk.

Claims

請求の範囲 The scope of the claims
1. 少なくとも光照射面 （読み取り面） にハードコー ト層を形成した光ディスクにおいて、 該ハードコート 層が次式 （ I 〉 1. In an optical disc having a hard coat layer formed on at least the light irradiation surface (read surface), the hard coat layer is expressed by the following formula (I>
R1 R2 R 1 R 2
CH2 =C- C0(0CH2 CH) n OH ·■■ ( I ) CH 2 = C- C0 (0CH 2 CH) n OH
〔式中、 R1 , R2 は水素原子またはメチル基を、 nは 1〜23の整数を示す。 〕 [In the formula, R 1 and R 2 represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 23. ]
で表されるポリエチレングリコ一ルまたはポリアロピ レングリコールのモノ 〈メタ） アクリル酸エステルの 少なくとも 1種を含有する硬化性樹脂組成物を硬化し てなる帯電防止性の塗膜であることを特徴とする光デ イスク。  Characterized in that it is an antistatic coating film obtained by curing a curable resin composition containing at least one mono (meth) acrylate ester of polyethylene glycol or poly (propylene glycol) represented by Light disk.
2. 前記硬化性樹脂組成物の前記ポリエチレンダリコ ールまたはポリプロピレングリコールのモノ （メタ〉 アクリル酸エステルの含有量が 5〜70重量％である 請求の範囲第 1項記載の光ディスク。  2. The optical disc according to claim 1, wherein the curable resin composition has a content of the mono (meth) acrylate of polyethylene diol or polypropylene glycol of 5 to 70% by weight.
3 - 前記硬化性樹脂組成物が、 3-the curable resin composition,
( a ) nが 4〜 6の前記ポリエチレンダリコ一ルお よびポリプロピレングリコールのモノ （メタ） ァク リル酸エステルの少なくとも 1種を 20〜 40重量
Figure imgf000052_0001
(a) 20 to 40% by weight of at least one of the above-mentioned polyethylene diol and polypropylene glycol mono (meth) acrylate having n of 4 to 6;
Figure imgf000052_0001
( b ) ジペンタエリスリ トールへキサ （メタ） ァク リレー卜またはその力アロラクトン変性体の少なく とも 1種を 4 0〜8 0重量％、  (b) 40 to 80% by weight of at least one of dipentaerythritol hexa (meth) acrylate or a modified allolactone thereof,
( c ) 成分 （ a〉 、 〈 b ) 以外の重合性希釈剤を必 要に応じて 0〜4 0重量％、  (c) 0 to 40% by weight of a polymerizable diluent other than the components (a) and <b), if necessary,
( d ) 重合開始剤を成分 （ a〉 、 （ b 〉 、 （ c 〉 の 合計量に対して 1〜1 0重量％  (d) The polymerization initiator is used in an amount of 1 to 10% by weight based on the total amount of the components (a), (b>, and (c).
合んでなる硬化性樹脂組成物である請求の範囲第 2項 記載の光ディスク。 3. The optical disc according to claim 2, wherein the optical disc is a curable resin composition obtained by combining the two.
. 前記硬化性樹脂組成物が、 The curable resin composition is
( a ) 式 （ェ 〉 で表されるポリエチレンダリコール またはポリプロピレングリコ一ルのモノ （メタ〉 ァ クリル酸エステルの少なくとも 1種を 3〜 4 0重量 (a) At least one kind of mono (meth) acrylic acid ester of polyethylene daricol or polypropylene glycol represented by the formula (e) is used in an amount of 3 to 40% by weight.
%、 %,
( e ) 陰イオン系界面活性剤を成分 （ a ) に対して (e) Anionic surfactant is added to component (a)
〇 . 0 1〜2 0 ϋ重量％ 〇. 0 1 ~ 20 ϋ% by weight
含有し、 且つ成分 〈 a ) 、 ( e ) の合計含有量が 5 〇 望量％以下である硬化性樹脂組成物である請求の範囲 第 ] 項記載の光ディスク ,， The optical disc according to claim 1, wherein the curable resin composition is a curable resin composition containing the components <a) and (e) in a total content of 5% or less.
. 前 te硬化性樹脂組成物が、  Before the te-curable resin composition,
( a ) riが 4〜 6の前記ポリエチレングリコールお よびポリプロピレングリコ一ルのモノ （メタ） ァク リル酸エステルの少なくとも 1種を 3〜4 0重量？ ό ( b ) ジペンタエリスリ トールへキサ （メタ〉 ァク リレートまたはそのカブ口ラク トン変性体の少なく とも 1種を 4 0〜8◦重量％、 (a) 3 to 40% by weight of at least one of the above-mentioned mono (meth) acrylates of polyethylene glycol and polypropylene glycol having ri of 4 to 6; ό (b) at least one of dipentaerythritol hexyl (meta) acrylate or a modified lactone lactone thereof at 40 to 8% by weight;
( c ) 成分 （ a〉 、 （ b 〉 以外の重合性希积剤を必 要に応じて 0〜4 0重量％、  (c) A polymerizable diluent other than the components (a> and (b>) may be added in an amount of 0 to 40% by weight, if necessary.
( d ) 重合開始剤を成分 （ a ) 、 （ b ) および （ c ) の合計重量に対して 1〜 1 0重量％、  (d) 1 to 10% by weight of the polymerization initiator based on the total weight of the components (a), (b) and (c),
( e ) 陰イオン系界面活性剤を成分 〈 a ) 、 ( b ) および （ c 〉 の合計重量に対して ϋ . 0 0 1〜 1 〇 舍んでなる硬化性樹脂組成物である請求の範囲第 4項 記載の光ディスク。  (e) a curable resin composition comprising an anionic surfactant in an amount of about 0.001 to 1% based on the total weight of the components <a), (b) and (c). Optical disc according to item 4.
- 成分 （ b ) が力プロラクトン変性のジペンタエリ スリ トールへキサ （メタ〉 アタリレートである請求の 範囲第 3項または第 5項記載の光ディスク。  -The optical disk according to claim 3 or 5, wherein the component (b) is dipentaerythritol hexa (meta) acrylate which is modified with force prolactone.
. 成分 （ c 〉 の重合性希釈剤がへキサメチレングリ コールジァクリレ一卜及び Zまたはテトラヒ ドロフル フリルァクリレートである請求の範囲第 1項〜第ら項 記載のいずれかの光ディスク The optical disc according to any one of claims 1 to 3, wherein the polymerizable diluent of the component (c) is hexamethylene glycol diacrylate and Z or tetrahydrofurfuryl acrylate.
. 成分 （ e 〉 の陰ィオン系界面活性剤がスルホン酸 の塩化合物及び./'または硫酸エステルの塩化合物で ある請求の範囲第 4項または第 5項記載の光ディス ク。 The optical disc according to claim 4 or 5, wherein the anionic surfactant of the component (e) is a salt compound of sulfonic acid and / or a salt compound of sulfate ester.
. 少なくとも光照射面 （読み取り面） にハ一ドコ一 ト層を形成した光ディスクにおいて、 該ハ一ドコート 層が次式 ( I ) At least a hard surface on the light irradiation surface (reading surface) In the optical disc having a hard coat layer formed thereon, the hard coat layer has the following formula (I)
R1 R2 R 1 R 2
CH2 =C- C0(0CH2 CH}n OR3- - ( E ) CH 2 = C- C0 (0CH 2 CH} n OR 3 --(E)
〔式中、 R1 , R2 は水素原子またはメチル基を、 H3 は炭素数 1〜9のアルキル基、 フエ二ル基、 炭素数 1〜9のアルキル基で置換されたフエニル 基、 炭素数 1〜9のアルコキシ基で置換されたフ ェニル基を、 nは 5〜23の整数を示す。 ：] で表されるポリエチレングリコールまたはポリアロピ レングリコールのモノ （メタ） アクリル酸エステルの エーテル誘導体の少なくとも 1種を 5〜70重量％含 有する硬化性樹脂組成物を.硬化してなる帯電防止性の 塗膜であることを特徴とする光ディスク。 Wherein R 1 and R 2 represent a hydrogen atom or a methyl group, H 3 represents an alkyl group having 1 to 9 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 9 carbon atoms, A phenyl group substituted with an alkoxy group of numbers 1 to 9, and n represents an integer of 5 to 23. :] An antistatic property obtained by curing a curable resin composition containing 5 to 70% by weight of at least one ether derivative of a mono (meth) acrylic acid ester of polyethylene glycol or polypropylene glycol represented by the formula: An optical disc characterized by being a coating film.
0. 少なくとも光照射面 （読み取り面〉 にハードコ 一ト層を形成した光ディスクにおいて、 該ハードコ一 卜層が次式 （ H )  0. In an optical disc having a hard coat layer formed on at least a light irradiation surface (reading surface), the hard coat layer has the following formula (H)
R1 R2 R 1 R 2
[CH2 =C- C0{0CH2 CH)a ] m 0P(0H)3-m … （ HI ) [CH 2 = C- C0 {0CH 2 CH) a] m 0P (0H) 3 - m … (HI)
〔式中、 R1 , R2 は水素原子またはメチル基を、 nは 1〜23の整数、 mは 1または 2の整数を示 す。 〕 [Wherein R 1 and R 2 represent a hydrogen atom or a methyl group, n is an integer of 1 to 23, and m is an integer of 1 or 2. ]
で表されるポリエチレングリコールまたはポリアロピ レンダリコールのモノ （メタ） アクリル酸エステルの モノ、 ジ燐酸エステル化合物を 0. 1〜60重量％含 有する硬化性樹脂組成物を硬化してなる帯電防止性の 塗膜であることを特徴とする光ディスク。  An antistatic coating obtained by curing a curable resin composition containing 0.1 to 60% by weight of a mono (meth) acrylate mono- or diphosphate compound of polyethylene glycol or polyalloyrene glycol represented by the formula: An optical disc characterized by being a film.
1. 前記硬化性樹脂組成物が、 次式 （ IV )  1. The curable resin composition has the following formula (IV)
R1 R 1
CH2 =C-C00CH2 CH2 0P(0H}2 … （ IV ) CH 2 = C-C00CH 2 CH 2 0P (0H) 2 … (IV)
〔式中、 R1 は水素原子またはメチル基〕 (In the formula, R 1 is a hydrogen atom or a methyl group.)
で表されるエチレングリコールモノ （メタ） アクリル 酸エステルの燐酸モノエステル化合物と有機アミン化 合物の 1 ： 1付加物を 0. 1〜20重量％含有する硬 化性樹脂組成物である請求の範囲第 1 0項記載の光デ イスク。 A curable resin composition containing 0.1 to 20% by weight of a 1: 1 adduct of a phosphoric acid monoester compound of ethylene glycol mono (meth) acrylate and an organic amine compound represented by the formula: The optical disk according to item 10 above.
2. 前記硬化性樹脂組成物を硬化してなる塗膜の鉛 箪硬度が HB以上であり、 かつ、 表面抵抗が 1 015Ω 7ロ未満である請求の範囲第 1項〜第 1 1項記載のい ずれかの光ディスク。 2. The lead film hardness of the coating film obtained by curing the curable resin composition is HB or more, and the surface resistance is less than 10 15 Ω 7 B. Any of the listed optical disks.
PCT/JP1991/000886 1990-07-02 1991-07-01 Optical disk WO1992000588A1 (en)

Applications Claiming Priority (14)

Application Number Priority Date Filing Date Title
JP2172655A JPH0467328A (en) 1990-07-02 1990-07-02 Optical disk
JP2/172658 1990-07-02
JP2172657A JPH0467330A (en) 1990-07-02 1990-07-02 Optical disk
JP2172658A JPH0467331A (en) 1990-07-02 1990-07-02 Optical disk
JP2/172656 1990-07-02
JP2172656A JPH0467329A (en) 1990-07-02 1990-07-02 Optical disk
JP2/172657 1990-07-02
JP2/172655 1990-07-02
JP3/33368 1991-02-04
JP3033371A JPH04247338A (en) 1991-02-04 1991-02-04 Optical disk
JP3/33371 1991-02-04
JP3/33369 1991-02-04
JP3033369A JPH04247337A (en) 1991-02-04 1991-02-04 Optical disk
JP3033368A JPH04247336A (en) 1991-02-04 1991-02-04 Optical disk

Publications (1)

Publication Number Publication Date
WO1992000588A1 true WO1992000588A1 (en) 1992-01-09

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7205105B2 (en) 1999-12-08 2007-04-17 Epoch Biosciences, Inc. Real-time linear detection probes: sensitive 5′-minor groove binder-containing probes for PCR analysis
US7348146B2 (en) 2003-10-02 2008-03-25 Epoch Biosciences, Inc. Single nucleotide polymorphism analysis of highly polymorphic target sequences
US7759126B2 (en) 2003-10-28 2010-07-20 Elitech Holding B.V. Real-time linear detection probes: sensitive 5′-minor groove binder-containing probes for amplification (or PCR) analysis
CN102741928A (en) * 2010-01-29 2012-10-17 日本化药株式会社 Optical disc having organic pigment recording layer, and UV-curable resin composition therefor

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5622364A (en) * 1979-08-01 1981-03-02 Matsushita Electric Ind Co Ltd Coating composition
JPS59168946A (en) * 1983-03-16 1984-09-22 Matsushita Electric Ind Co Ltd Optical disc
JPS6254770A (en) * 1985-07-31 1987-03-10 イ−・アイ・デユポン・ドウ・ヌム−ル・アンド・カンパニ− Optical coating composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5622364A (en) * 1979-08-01 1981-03-02 Matsushita Electric Ind Co Ltd Coating composition
JPS59168946A (en) * 1983-03-16 1984-09-22 Matsushita Electric Ind Co Ltd Optical disc
JPS6254770A (en) * 1985-07-31 1987-03-10 イ−・アイ・デユポン・ドウ・ヌム−ル・アンド・カンパニ− Optical coating composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7205105B2 (en) 1999-12-08 2007-04-17 Epoch Biosciences, Inc. Real-time linear detection probes: sensitive 5′-minor groove binder-containing probes for PCR analysis
US7485442B2 (en) 1999-12-08 2009-02-03 Epoch Biosciences, Inc. Real-time linear detection probes: sensitive 5'-minor groove binder-containing probes for PCR analysis
US7348146B2 (en) 2003-10-02 2008-03-25 Epoch Biosciences, Inc. Single nucleotide polymorphism analysis of highly polymorphic target sequences
US7718374B2 (en) 2003-10-02 2010-05-18 Elitech Holding B.V. Single nucleotide polymorphism analysis of highly polymorphic target sequences
US7759126B2 (en) 2003-10-28 2010-07-20 Elitech Holding B.V. Real-time linear detection probes: sensitive 5′-minor groove binder-containing probes for amplification (or PCR) analysis
CN102741928A (en) * 2010-01-29 2012-10-17 日本化药株式会社 Optical disc having organic pigment recording layer, and UV-curable resin composition therefor

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